Copolymerizable methine and anthraquinone compounds and articles containing them

ABSTRACT

This invention relates to polymerizable ultraviolet light absorbers and yellow colorants and their use in ophthalmic lenses. In particular, this invention relates to polymerizable ultraviolet light absorbing methane compounds and yellow compounds of the methine and anthraquinone classes that block ultraviolet light and/or violet-blue light transmission through ophthalmic lenses.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.12/257,277, now U.S. Pat. No. ______, which is a continuation of U.S.patent application Ser. No. 11/271,382 filed on Nov. 10, 2005, whichclaims the benefit of U.S. provisional patent application No. 60/629,556filed Nov. 22, 2004, all aforementioned documents are incorporatedherein by reference.

FIELD OF THE INVENTION

This invention relates to polymerizable ultraviolet light absorbers,yellow colorants and their use in ophthalmic lenses. In particular, thisinvention relates to polymerizable ultraviolet light absorbing methinecompounds and polymerizable yellow compounds of the methine andanthraquinone classes that block ultraviolet light and/or violet-bluelight transmission through ophthalmic lenses.

BACKGROUND OF THE INVENTION

The sun freely emits ultraviolet (UV), visible and infrared (IR)radiation, much of which is absorbed by the atmosphere. Solar radiationthat is transmitted through the atmosphere and reaches the earth'ssurface includes UV-A radiation (320-400 nm), UV-B radiation (290-320nm), visible light (400-700 nm) and near IR radiation (700-1400 nm). Theocular lens of humans in its normal, healthy state freely transmits nearIR and most of the visible spectrum to the retina, but the lens acts toabsorb UV radiation to avoid damage to the retina. The ability to absorbnear UV and the violet-blue portion of the visible spectrum changesthroughout life. In infancy, the human lens will freely transmit near UVand visible light above 300 nm, but with further aging the action of UVradiation from the environment causes the production of yellowcolorants, fluorogens, within the lens. Some studies indicate that byage 54 the lens will not transmit light below 400 nm and thetransmission of light between 400 and 450 nm is greatly diminished. Asthe lens ages it continuously develops a yellow color, increasing itscapacity to filter out near UV and violet-blue light. Therefore, aftercataract removal the natural protection provided by the aged human lensis also removed. Cataracts are typically replaced by an intraocular lens(IOL). If the brain is stimulated by signals caused by the visible lightthat has not been transmitted for many years, discomfort can result.Development of IOL materials with an absorption similar to aged humanlens material would be a welcome improvement to the art.

Although yellow colorants exist, many such colorants are unsuitable foruse in artificial lens material due to their tendency to leach out ofthe IOL after it is inserted in the eye or during solvent extractionassociated with lens manufacture. A yellow colorant that is covalentlybonded to lens materials would be thus be a desirable improvement in themanufacture of artificial lens materials. Efforts have been made todevelop such a lens material. One obstacle of such efforts has beenfinding a polymerizable compound that will produce IOLs having anabsorption profile that carefully matches that of the aged human lens,especially in the visible spectrum. If the IOL absorbs more than thelens in portions of the visible spectrum, visible acuity can bediminished. If the IOL absorbs less in the visible spectrum, thediscomfort discussed above can result. Another obstacle that suchefforts have faced has been the need to use a combination of multiplecompounds to achieve a careful match with the human lens. Use ofmultiple compounds can result in a more complicated manufacturingprocess, along with increased production and materials costs. Apolymerizable yellow colorant that matches the absorption spectra of thehuman lens and reduces the need for multiple colorants in an IOL wouldbe a welcome improvement in the art.

More broadly, the development of yellow colorants and absorbers ofultraviolet light that can be covalently bonded to various polymericmaterials would have numerous other uses beyond that in artificiallenses. For example, such colorants could be used with a wide array ofpolymeric applications in which the appropriate absorption spectrum isdesired. Thus, what is needed in the art is novel yellow colorants andultraviolet light absorbers (UVAs) that are more economical, and havespectral properties that better suit their target applications.

SUMMARY OF THE INVENTION

The invention solves the problems in the prior art by providingmolecules that contain methine chromophores and/or anthraquinonechromophores and ethylenically-unsaturated polymerizable groups. Thesechromophores are present as structures that include at least one of thefollowing moieties:

wherein X is selected from hydrogen or one or two groups selected fromhydroxy, C₁-C₆ alkyl, C₁-C₆ alkoxy and halogen. The molecules of thepresent invention contain these moieties as well as at least oneethylenically-unsaturated polymerizable group that is capable ofundergoing free radical polymerization without destroying the moiety.The ethylenically-unsaturated polymerizable group exists in addition toany such group that appears in the above figures. Thus, in the case ofstructure 1a, the resulting molecule contains at least one polymerizableethylenically unsaturated group in addition to the ethylenicallyunsaturated group(s) depicted. It is to be understood that thesemoieties are only portions of the molecules and that the moleculescontain additional moieties. Thus for example, in some embodiments themolecule of the present invention is one of the compounds represented byFormulae II-VI below:

wherein:R and R₁ are independently selected from C₁-C₁₂-alkyl, substitutedC₁-C₁₂-alkyl, aryl, heteroaryl, C₃-C₈-cycloalkyl, C₃-C₈-alkenyl,—(CHR′CHR″O—)_(n)—R₄, C₁-C₆-alkylsulfonyl, arylsulfonyl, C₁-C₁₂-acyl,substituted-C₁-C₁₂-acyl, -L-Q and -Q; R and R₁ can be combined to makecyclic structures such as phthalimido, succinimido, morpholino,thiomorpholino, pyrrolidino, piperidino, piperazino,thiomorpholino-S,S-dioxide and the like;n is an integer selected from 1 to about 1000;R₂ is selected from hydrogen or one or two groups selected from hydroxy,C₁-C₆ alkyl, C₁-C₆ alkoxy and halogen;R₃ is selected from hydrogen, C₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl,aryl, C₃-C₈-cycloalkyl, C₃-C₈-alkenyl and —(CHR′CHR″O—)_(n)—R₄,C₁-C₁₂-acyl, substituted-C₁-C₁₂-acyl, -L-Q and Q;R₄ is selected from hydrogen, C₁-C₁₂-alkyl, C₁-C₆-alkanoyl and aryl;R′ and R″ are independently selected from hydrogen and C₁-C₁₂-alkyl;L is a divalent organic radical selected from C₁-C₆-alkylene-O—,C₁-C₆-alkylene-NR′—; arylene-C₁-C₆-alkylene-O—,arylene-C₁-C₆-alkylene-NR′—, arylene-O(CHR′CHR″O)_(n)—,C₁-C₆-alkylene-Y₁—(CHR′CHR″O—)_(n)—, —(CHR′CHR″O—)_(n)—;Y is selected from —O-L-Q, —NR′-L-Q, —N-(L-Q)₂, —R₅;Y₁ is selected from —O—, —S—, —SO₂—, —N(SO₂R₅)—, or —N(COR₅)—;R₅ is C₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl, C₃-C₈-cycloalkyl or aryl;X₁ and X₂ are independently selected from cyano, C₁-C₆-alkoxycarbonyl,C₁-C₆-alkylsulfonyl, arylsulfonyl, carbamoyl, C₁-C₆-alkanoyl, aroyl,aryl, heteroaryl and —COY;Q is a group that includes an ethylenically-unsaturated polymerizablegroup;wherein the compound comprises or has bonded thereto at least one Qgroup.

As can be seen, Formula II depicts a molecule containing moiety 1c.Formula III depicts a molecule containing moiety 1b. Formula IV depictsa molecule containing moiety 1a. Formulae V and VI depict moleculescontaining moiety 1d.

It will be understood that the location of atoms bonded to the carbonsin any ethene double bond in Formulas II, III, and IV should not beinterpreted as limiting and that Formulas II, III, and IV should beinterpreted as including both cis and trans stereoisomers throughoutthis application, including the claims.

In some embodiments, the compounds of the present invention arepolymerized with other molecules capable of polymerizing to form apolymer in which the compounds are part of the backbone. In someembodiments, the compounds are polymerized with organic monomers to forma material that is transparent to visible light, or that has a degree ofabsorption or transparency to various light wavelengths that mimics thatof a desired material, such as the lens of a mammalian eye of a givenage. However, the invention includes all types of polymers irrespectiveof the degree of transparency, translucency, or opacity to any type ofradiation.

By bonding the compound to the polymer, the potential for the compoundleaching out of the material is diminished or eliminated. As a result,in some embodiments these compounds are used in transparent materials todecrease the intensity of violet-blue light transmitted through them.These transparent materials with one or more of the bondable yellowcompounds and/or bondable UVAs incorporated in them may be extractedwith organic solvents to remove unreacted monomers, low molecular weightoligomers and low molecular weight polymers, as well as otherimpurities, and then used to make ocular lenses such as intraocularlenses (IOLs), contact lenses, eyeglasses and other windows. Thesetransparent materials containing yellow compounds may also be used tomake lens coating materials. Surprisingly, the methine chromophores ofthe present invention do not lose their absorbance properties upon freeradical polymerization. This is surprising since the chromophoric unitis an ethylenically unsaturated moiety so that the polymerizationreaction involving the chromophoric unit would be expected to result inloss of the absorption properties.

Thus, the invention includes the compounds disclosed herein.

The invention further includes compositions comprising the compounds ofthe present invention. In some embodiments, the compositions arepolymerizable compositions.

The invention further includes methods of making a polymer comprisingpolymerizing a group of monomers, prepolymers, chain extenders, orcombinations of thereof, one or more of which contains a compound of thepresent invention or a residue of such a compound.

The invention further includes polymers that contain the residue of thepolymerization of the compounds of the present invention.

The invention further includes articles that contain the polymers of thepresent invention. In some embodiments, the articles are transparent. Insome embodiments, the articles are optical objects. In some embodiments,the articles are IOLs.

DETAILED DESCRIPTION OF THE INVENTION

Polymerizable yellow compounds and UV absorbing compounds that are basedon the methine and anthraquinone chromophores and contain polymerizable,ethylenically unsaturated moieties are provided. The invention furtherincludes compositions comprising the compounds of the present invention.In some embodiments, the compositions are polymerizable compositions.The invention further includes methods of making a polymer comprisingpolymerizing a group of monomers, prepolymers, chain extenders, orcombinations of thereof, one or more of which contains a compound of thepresent invention or a residue of such a compound. The invention furtherincludes polymers that contain the residue of the polymerization of thecompounds of the present invention. The invention further includesarticles that contain the polymers of the present invention. In someembodiments, the articles are transparent. In some embodiments, thearticles are optical objects. In some embodiments, the articles areIOLs.

DEFINITIONS

The following definitions apply to terms as used throughout thisapplication.

The term “chromophoric unit” means the portion of a molecule primarilyresponsible for causing the absorption of radiation at the wavelength ofmaximum absorption.

The alkyl groups described by the terms “C₁-C₆-alkyl” and “C₁-C₆ alkoxy”refer to straight or branched chain hydrocarbon radicals containing oneto six carbon atoms optionally substituted with hydroxy, cyano, aryl,—OC₁-C₄-alkyl, —OCOC₁-C₄-alkyl and —CO₂C₁-C₄-alkyl, wherein theC₁-C₄-alkyl portion of the groups represents a saturated straight orbranched chain hydrocarbon radical that contains one to four carbonatoms.

The alkyl groups described by the term “C₁-C₁₂-alkyl” refer to straightor branched chain hydrocarbon radicals containing one to twelve carbonatoms.

The terms “C₁-C₁₂-acyl” and “substituted-C₁-C₁₂-acyl” are used torepresent —CO—(C₁-C₁₂-alkyl) and —CO-(substituted C₁-C₁₂-alkyl),respectively.

The term “C₃-C₈-cycloalkyl” refers to a cyclic hydrocarbon radicalcontaining three to eight carbon atoms.

The term “aryl” includes phenyl and naphthyl and these radicalssubstituted with one to three C₁-C₆-alkyl, C₁-C₆-alkoxy, —CN, —NO₂,C₁-C₆-alkoxycarbonyl, C₁-C₆-alkanoyloxy, C₁-C₆— alkylsulfonyl, hydroxyl,carboxy or halogen groups.

The term “heteroaryl” includes 5 or 6-membered heterocyclic aryl ringscontaining one oxygen atom, and/or one sulfur atom, and up to threenitrogen atoms, said heterocyclic aryl ring optionally fused to one ortwo phenyl rings. Examples of such systems include thienyl, furyl,pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl,isoxazolyl, triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl,thiatriazolyl, oxatriazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl,thiazinyl, oxazinyl, triazinyl, thiadiazinyl, oxadiazinyl, dithiazinyl,dioxazinyl, oxathiazinyl, tetrazinyl, thiatriazinyl, oxatriazinyl,dithiadiazinyl, imidazolinyl, dihydropyrimidyl, tetrahydropyrimidyl,tetrazolo-[1,5-b]pyridazinyl and purinyl, benzoxazolyl, benzothiazolyl,benzimidazolyl, indolyl and the like; these are optionally substitutedwith one to three C₁-C₆-alkyl, aryl, C₁-C₆-alkoxy, —CN, —NO₂,C₁-C₆-alkoxycarbonyl, C₁-C₆-alkanoyloxy, C₁-C₆-alkylsulfonyl or halogengroups.

The term “substituted-C₁-C₁₂-alkyl” is used herein to denote a straightor branched chain, saturated aliphatic hydrocarbon radical containingone to twelve carbon atoms and these radicals optionally substitutedwith one to three groups selected from hydroxy; halogen; cyano;succinimido; glutarimido; phthalimido; 2-pyrrolidono; aryl; heteroaryl;heteroarylthio; aryloxy; arylthio; C₁-C₆-alkoxy, C₁-C₆-alkylthio;C₁-C₆-alkylsulfonyl; arylsulfonyl; sulfamyl; benzoylsulfonicimido;C₁-C₆-alkylsulfonamido; arylsulfonamido; C₃-C₈-alkenylcarbonylamino;—NR′-L-Q; —N-(L-Q)₂; —O-L-Q; groups of the formula

wherein Y₂ is —NH—, —N(C₁-C₁₂-alkyl)-, —O—, —S—, or —CH₂O—; —OX₃R₁₂,—NHX₃R₁₂; —CONR₁₃R′₁₃; —SO₂NR₁₃R′₁₃; wherein R₁₂ is selected fromC₁-C₁₂-alkyl and C₁-C₆-alkyl substituted with halogen, phenoxy, aryl,cyano, C₃-C₈-cycloalkyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylthio, andC₁-C₆-alkoxy; R₁₃ and R′₁₃ are independently selected from hydrogen,aryl, C₁-C₁₂-alkyl and C₁-C₆-alkyl substituted with halogen, phenoxy,aryl, —CN, cyclolalkyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylthio, orC₁-C₆-alkoxy; X₃ is selected from —CO—, —COO—, —CONH—, or —SO₂—;C₃-C₈-cycloalklyl; C₁-C₆-alkanoyloxy; C₁-C₆-alkoxycarbonyl and—(O—C₂-C₄-alkylene)_(n)R₁₄; wherein R₁₄ is selected from hydrogen,C₁-C₆-alkoxy, halogen, hydroxy, cyano, C₁-C₆-alkanoyloxy,C₁-C₆-alkoxycarbonyl, aryl, C₃-C₈-cycloalkyl; and —OQ; n is aspreviously defined.

The term “C₁-C₆-alkylene” refers to a straight or branched chain,divalent hydrocarbon radical containing one to six carbon atoms andoptionally substituted with hydroxy, halogen, aryl, C₁-C₆-alkanoyloxy,or —OQ.

The term “halogen” means any of the following atoms: fluorine, chlorine,bromine and iodine.

The terms “C₁-C₆-alkoxycarbonyl” and “C₁-C₆-alkanoyloxy” denote theradicals —CO₂C₁-C₆-alkyl and —O—COC₁-C₆-alkyl, respectively.

The term “C₃-C₈ alkenyl” denotes a straight or branched chainhydrocarbon radical that contains at least one carbon-carbon doublebond.

In the terms “arylsulfonyl” and “aroyl” the aryl groups or aryl portionsof the groups are selected from phenyl and naphthyl, and these mayoptionally be substituted with hydroxy, halogen, carboxy, C₁-C₆-alkyl,C₁-C₆-alkoxy and C₁-C₆-alkoxycarbonyl.

The term “carbamoyl” is used to represent the group having the formula:—CON(R₁₅)R₁₆, wherein R₁₅ and R₁₆ are selected from hydrogen,C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₃-C₈-alkenyl, and aryl.

The term “C₁-C₆-alkylsulfonyl” is used to represent —SO₂—C₁-C₆-alkylwherein the term “C₁-C₆-alkyl” is as previously defined.

References herein to groups or moieties having a stated range of carbonatoms, such as “C₁-C₆-alkyl,” shall mean not only the C₁ group (methyl)and C₆ group (hexyl) end points, but also each of the correspondingindividual C₂, C₃, C₄ and C₅ groups. In addition, it will be understoodthat each of the individual points within a stated range of carbon atomsmay be further combined to describe subranges that are inherently withinthe stated overall range. For example, the term “C₃-C₈-cycloalkyl”includes not only the individual cyclic moieties C₃ through C₈, but alsocontemplates subranges such as “C₄-C₆-cycloalkyl.”

The phrase “ethylenically-unsaturated polymerizable group” and/or “freeradical initiated polymerizable group” shall mean a moiety having a C═Cdouble bond that is reactive in a free radical polymerization, includingbut not limited to those having a vinyl group. In some embodiments, thereactive double bond is activated by one of the double-bonded carbonsbeing attached to an aryl group or an electron withdrawing group such asa carbonyl. Although aromatic and heteroaromatic rings are often drawnin this application and elsewhere in a way that depicts the aromatic picloud of electrons in such rings as alternating double bonds (forexample, benzene is often drawn as a six membered ring containing threealternating double and single bonds) the skilled artisan will understandthat such rings do not actually contain double bonds but instead containan aromatic pi cloud of completely delocalized electrons and, as such,are unreactive to free radical polymerization. Accordingly, none of theterms “reactive C═C double bond,” “ethylenically-unsaturatedpolymerizable group,” and “free radical initiated polymerizable group”include aromatic pi clouds of electrons in aromatic or heteroaromaticring, irrespective of whether such aromatic pi clouds of electrons arerepresenting in any drawing as alternating double bonds.

Compounds

The compounds are molecules that include at least one of the followingmoieties:

wherein X is selected from hydrogen or one or two groups selected fromhydroxy, C₁-C₆ alkyl, C₁-C₆ alkoxy and halogen. The molecules of thepresent invention contain these moieties as well as at least oneethylenically-unsaturated polymerizable group that is capable ofundergoing free radical polymerization without destroying the moiety.The ethylenically-unsaturated polymerizable group exists in addition toany such group that appears in the above figures. Thus, in the case ofstructure 1a, the resulting molecule contains at least one polymerizableethylenically unsaturated group in addition to the ethylenicallyunsaturated group(s) depicted. It is to be understood that thesemoieties are only portions of the molecules and that the moleculescontain additional moieties. Thus, for example, in some embodiments themolecule of the present invention is one of the compounds represented byFormulae II-VI below:

wherein:R and R₁ are independently selected from C₁-C₁₂-alkyl, substitutedC₁-C₁₂-alkyl, aryl, heteroaryl, C₃-C₈-cycloalkyl, C₃-C₈-alkenyl,—(CHR′CHR″O—)_(n)—R₄, C₁-C₆-alkylsulfonyl, arylsulfonyl, C₁-C₁₂-acyl,substituted-C₁-C₁₂-acyl, -L-Q and -Q; R and R₁ can be combined to makecyclic structures such as phthalimido, succinimido, morpholino,thiomorpholino, pyrrolidino, piperidino, piperazino,thiomorpholino-S,S-dioxide and the like;n is an integer selected from 1 to about 1000;R₂ is selected from hydrogen or one or two groups selected from hydroxy,C₁-C₆ alkyl, C₁-C₆ alkoxy and halogen;R₃ is selected from hydrogen, C₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl,aryl, C₃-C₈-cycloalkyl, C₃-C₈-alkenyl and —(CHR′CHR″O—)_(n)—R₄,C₁-C₁₂-acyl, substituted-C₁-C₁₂-acyl, -L-Q and Q;R₄ is selected from hydrogen, C₁-C₁₂-alkyl, C₁-C₆-alkanoyl and aryl;R′ and R″ are independently selected from hydrogen and C₁-C₁₂-alkyl;L is a divalent organic radical selected from C₁-C₆-alkylene-O—,C₁-C₆-alkylene-NR—; arylene-C₁-C₆-alkylene-O—,arylene-C₁-C₆-alkylene-NR—, arylene-O(CHR′CHR″O)_(n)—,C₁-C₆-alkylene-Y₁—(CHR′CHR″O—)_(n)—, —(CHR′CHR″O—)_(n)—;Y is selected from —O-L-Q, —NR′-L-Q, —N-(L-Q)₂, —R₅;Y₁ is selected from —O—, —S—, —SO₂—, —N(SO₂R₅)—, or —N(COR₅)—;R₅ is C₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl, C₃-C₈-cycloalkyl or aryl;X₁ and X₂ are independently selected from cyano, C₁-C₆-alkoxycarbonyl,C₁-C₆-alkylsulfonyl, arylsulfonyl, carbamoyl, C₁-C₆-alkanoyl, aroyl,aryl, heteroaryl and —COY;Q is a group that includes an ethylenically-unsaturated polymerizablegroup;wherein the compound includes at least one Q group.

As can be seen, Formula II depicts examples of a molecule containingmoiety 1c. Formula III depicts examples of a molecule containing moiety1b. Formula IV depicts examples of a molecule containing moiety 1a.Formulae V and VI depict examples of molecules containing moiety 1d.

It will be understood that the location of atoms bonded to the carbonsin any ethene double bond in Formulas II, III, and IV should not beinterpreted as limiting and that Formulas II, III, and IV should beinterpreted as including both cis and trans stereoisomers throughoutthis application, including the claims.

In some embodiments, the alkoxylated moiety of R, R₁, R₃ and L includeeither ethylene oxide or propylene oxide, or mixtures of both, thereonhaving a chain length denoted by the formula wherein n is from 1 toabout 100. In some embodiments, the chain length is denoted by theformula wherein n is less than 50. In some embodiments, the chain lengthis denoted by the formula wherein n is less than about 8.

Examples of Q groups include but are not limited to the followingorganic radicals 1-9:

or a combination of the two structures on a plurality of compounds;wherein:

R₆ is hydrogen or C₁-C₆-alkyl;

R₇ is: hydrogen; C₁-C₆ alkyl; phenyl; phenyl substituted with one ormore groups selected from C₁-C₆-alkyl, C₁-C₆-alkoxy, —N(C₁-C₆-alkyl)₂,nitro, cyano, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkanoyloxy and halogen; 1- or2-naphthyl; 1- or 2-naphthyl substituted with C₁-C₆-alkyl orC₁-C₆-alkoxy; 2- or 3-thienyl; 2- or 3-thienyl substituted withC₁-C₆-alkyl or halogen; 2- or 3-furyl; or 2- or 3-furyl substituted withC₁-C₆-alkyl;

R₈ and R₉ are, independently, hydrogen, C₁-C₆-alkyl, or aryl; or R₈ andR₉ are combined to form a CH₂₃₋₅ radical;

R₁₀ is hydrogen, C₁-C₆-alkyl, C₁-C₈-alkenyl, C₃-C₈-cycloalkyl or aryl;and

R₁₁ is hydrogen, C₁-C₆-alkyl or aryl.

In some embodiments, a compound of Formulae II, III, IV, V or VI is usedin which Q is

wherein R₆ is hydrogen or methyl and R₈ and R₉ are methyl.

In some embodiments, a compound of Formulae II, III, IV, V or VI is usedin which Q is:

—C(O)C(R₆)═CHR₇

wherein R₆ is hydrogen or methyl; and R₇ is hydrogen.

In some embodiments compound has a structural formula consistent withFormula II in which: R and R₁ are independently selected fromC₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl, aryl, heteroaryl,C₃-C₈-cycloalkyl, C₃-C₈-alkenyl, —(CHR′CHR″O—)_(n)—R₄,C₁-C₆-alkylsulfonyl, arylsulfonyl, C₁-C₁₂-acyl, substituted-C₁-C₁₂-acyl,-L-Q and -Q; R and R₁ can be combined to make cyclic structures such asphthalimido, succinimido, morpholino, thiomorpholino, pyrrolidino,piperidino, piperazino, thiomorpholino-S,S-dioxide and the like;

n is an integer selected from 1 to about 1000;R₂ is selected from hydrogen or one or two groups selected from hydroxy,C₁-C₆ alkyl, C₁-C₆ alkoxy and halogen;R′ and R″ are independently selected from hydrogen and C₁-C₁₂-alkyl;L is a divalent organic radical selected from C₁-C₆-alkylene-O—,C₁-C₆-alkylene-NR—; arylene-C₁-C₆-alkylene-O—,arylene-C₁-C₆-alkylene-NR—, arylene-O(CHR′CHR″O)_(n)—,C₁-C₆-alkylene-Y₁—(CHR′CHR″O—)_(n)—, —(CHR′CHR″O—)_(n)—;Y is selected from —O-L-Q, —NR′-L-Q, —N-(L-Q)₂, —R₅;Y₁ is selected from —O—, —S—, —SO₂—, —N(SO₂R₅)—, or —N(COR₅)—;R₄ is selected from hydrogen, C₁-C₁₂-alkyl, C₁-C₆-alkanoyl and aryl;R₅ is C₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl, C₃-C₈-cycloalkyl or aryl;X₁ and X₂ are independently selected from cyano, —CO₂C₁-C₆-alkyl,C₁-C₆-alkylsulfonyl, arylsulfonyl, carbamoyl, C₁-C₆-alkanoyl, aroyl,aryl, heteroaryl and —COY;Q is a group that includes an ethylenically-unsaturated polymerizablegroup; the compound comprises or has bonded thereto at least one Qgroup.

In some embodiments the compound is a compound of Formula II wherein Rand R₁ are independently selected from —CH₂CH₂CN, —CH₂CH₂Cl,—CH₂CH₂—OCO—C₁-C₄-alkyl, —CH₂CH₂OCO-aryl, —CH₂CH₂—OC(O)NH-aryl,—C₁-C₄-alkyl, —CH₂C₆H₄CO₂—C₁-C₄-alkyl,

or combined to make the cyclic structure thiomorpholino-S,S-dioxide;Y is —NH-L-Q; L is —CH₂CH₂O—, —CH₂CH(CH₃)O—, —(CH₂)₃O—, —(CH₂)₄O—,—(CH₂)₆O—, —CH₂C(CH₃)₂CH₂O—, —CH₂—C₆H₁₀—CH₂O—, —C₆H₄—CH₂CH₂O—,—C₆H₄—OCH₂CH₂O—, —CH₂CH₂(OCH₂CH₂)₁₋₃O—, and

Q is

wherein R₆ is methyl; R₈ and R₉ are methyl.

In some embodiments the compound is a compound of Formula II wherein Rand R₁ are independently selected from —CH₂CH₂CN, —CH₂CH₂Cl,—CH₂CH₂—OCO—C₁-C₄-alkyl, —CH₂CH₂OCO-aryl, —CH₂CH₂—OC(O)NH-aryl,—C₁-C₄-alkyl, —CH₂C₆H₄CO₂—C₁-C₄-alkyl,

or combined to make the cyclic structure thiomorpholino-S,S-dioxide; Yis —NH-L-Q; L is —CH₂CH₂O—, —CH₂CH(CH₃)O, —(CH₂)₃O—, —(CH₂)₄O—,—(CH₂)₆O—, —CH₂C(CH₃)₂CH₂O—, —CH₂—C₆H₁₀—CH₂O—, —C₆H₄—CH₂CH₂O—,—C₆H₄—OCH₂CH₂O—, —CH₂CH₂(OCH₂CH₂)₁₋₃O—, and Q is:

—C(O)C(R₆)═CHR₇

wherein R₆ is methyl; and R₇ is hydrogen.

In some embodiments the compound is a compound of Formula II wherein Ris selected from —CH₂CH₂CN;

wherein R₁ is selected from —CH₂CH₂CN, —CH₂CH₂Cl,—CH₂CH₂OCO—C₁-C₄-alkyl,

Y is —NH-L-Q; L is —CH₂CH₂O—, —CH₂CH(CH₃)O—, and Q is

wherein R₆ is methyl; R₈ and R₉ are methyl.

In some embodiments the compound is a compound of Formula II wherein Ris selected from —CH₂CH₂CN; wherein R₁ is selected from —CH₂CH₂CN,—CH₂CH₂Cl, —CH₂CH₂OCO—C₁-C₄-alkyl,

Y is —NH-L-Q; L is —CH₂CH₂O—, —CH₂CH(CH₃)O—, and Q is:

—C(O)C(R₆)═CHR₇

wherein R₆ is methyl; and R₇ is hydrogen.

In some embodiments, the compounds of the present invention have anmaximum absorption less than 420 nm and have little if any absorption atwavelengths greater than about 450 nm at concentrations that aresuitable in the present invention. In some embodiments, the wavelengthat which maximum absorption occurs is between about 300 nm and about 420nm. In some embodiments, there is minimal absorption at 450 nm. In someembodiments, the wavelength of maximum absorption is between about 350nm and about 390 nm. In some embodiments, the wavelength of maximumabsorption is between about 370 nm and about 380 nm. In someembodiments, the wavelength of maximum absorption of the ultravioletlight absorber is between about 310 nm and about 375 nm. In someembodiments, the wavelength of maximum absorption the absorption of thechromophoric unit at wavelength greater than 400 nm is no more than 20percent of total absorption between about 330 nm and 450 nm.

Compositions Comprising the Compounds

Compositions comprising the compounds of the present invention are alsoprovided. The compound may be incorporated in a number of materials in avariety of applications where it is desirable to achieve certain desiredcolors or desired wavelength absorbances.

In some embodiments, the composition is a polymerizable compositioncontaining the compounds of the present invention. In some embodiments,the polymerizable composition contains an ultraviolet light absorbingmethine polymerizable compound in combination with a yellow methinepolymerizable compound and/or an anthraquinone polymerizable compound toobtain the correct shade of yellow while absorbing ultraviolet light inthe wavelength range of 300 nm to 400 nm. The amount of yellow compoundwill be determined by the application and the spectral properties of thecompound. The amount of yellow polymerizable compound may be determinedby the thickness of the films (or lens) and by the practitioner. In someembodiments, the amount of yellow polymerizable compound is less thanabout 4 weight percent based upon the total weight of the resultingpolymer. In some embodiments, the amount of yellow polymerizablecompound is less than about 4 weight percent based upon the total weightof the resulting polymer. In some embodiments, the amount of yellowpolymerizable compound is less than about 2 weight percent based uponthe total weight of the resulting polymer. In some embodiments, theamount of yellow polymerizable compound is less than about 1.5 weightpercent resulting polymer resulting polymer based upon the total weightof the resulting polymer. In some embodiments, the amount of yellowpolymerizable compound is less than about 1 weight percent based uponthe total weight of the resulting polymer. The ultraviolet lightabsorbing methine polymerizable compound will be added in sufficientamount to block the desired amount of ultraviolet light that penetratesthe polymer, which is determined by the thickness of the film and thepractitioner. In some embodiments, the amount of ultraviolet lightabsorbing polymerizable methine compound is less than about 4 weightpercent based upon the total weight of the resulting polymer. In someembodiments, the amount of ultraviolet light absorbing polyermizablemethine compound is less than about 2 weight percent based upon thetotal weight of the resulting polymer. In some embodiments, the amountof ultraviolet light absorbing polyermizable methine compound is lessthan about 1.5 weight percent based upon the total weight of theresulting polymer. In some embodiments, the amount of ultraviolet lightabsorbing polyermizable methine compound is less than about 1 weightpercent based upon the total weight of the resulting polymer. The weightpercentages in this paragraph are determined by dividing the weight ofcompound used in the polymerization by the total weight of the resultingpolymer (multiplied by 100 percent).

In some embodiments, the polymerizable composition contains otherultra-violet absorbing compounds in addition to the compounds of thepresent invention. The ultraviolet absorbing material can be anycompound which absorbs light having a wavelength shorter than about 400nm but does not absorb any substantial amount of visible light. In someembodiments, the ultraviolet absorbing compound is incorporated into themonomer mixture and is entrapped in the polymer matrix when the monomermixture is polymerized. Suitable ultraviolet absorbing compounds includesubstituted benzophenones, such as 2-hydroxybenzophenone, and2-(2-hydroxyphenyl)benzotriazoles. In some embodiments, an ultravioletabsorbing compound which is copolymerizable with the monomers and isthereby covalently bound to the polymer matrix is used. In this way, therisk of leaching of the ultraviolet absorbing compound out of the lensand into the interior of the eye is reduced. Suitable copolymerizableultraviolet absorbing compounds are the substituted2-hydroxybenzophenones disclosed in U.S. Pat. No. 4,304,895 and the2-hydroxy-5-acryloxyphenyl-2H-benzotriazoles disclosed in U.S. Pat. No.4,528,311. In some embodiments, the ultraviolet absorbing compound2-(3′-methallyl-2′-hydroxy-5′methyl phenyl)benzotriazole, also known asortho-methallyl Tinuvin P (“oMTP”) is included in the polymerizablecomposition. Any and all combinations of the other components in thepolymerizable composition may be used.

Since some ultraviolet absorbing compounds have phenolic substituents orresidues within their structure that are known to inhibitpolymerization, it is sometimes advantageous to minimize the amount ofultraviolet absorbing compound in the polymerizable composition.Reducing the concentration of such ultraviolet absorbing compounds canbe beneficial to the lens forming process. In some embodiments involvingoMTP, that compound is present in a concentration of approximately 1.8wt. %. However, depending on the specific yellow compound chosen and thedesired transmission at a given wavelength, considerably less than 1.8wt. % of oMTP may be used. In some embodiments, the ultraviolet lightabsorbing polymerizable compounds are represented by Formula III whereinR₃ is selected from substituted C₁-C₁₂-alkyl and -LQ; R₂ is selectedfrom hydrogen, C₁-C₆-alkyl, and C₁-C₆-alkyoxy; X₁ is cyano; X₂ isselected from —CO₂—C₁-C₆-alkyl, —CONH—C₁-C₆-alkyl, —CN, —CONH-L-Q; L is—CH₂CH₂O—, —CH₂CH(CH₃)O—, —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₆—, —CH₂C(CH₃)₂CH₂—,—CH₂—C₆H₁₀—CH₂—, —C₆H₄—CH₂CH₂—, —C₆H₄—OCH₂CH₂—, —CH₂CH₂(OCH₂CH₂)₁₋₃— andQ is

wherein R′ is selected from hydrogen or methyl; R₆ is methyl; R₇ ishydrogen and R₈ and R₉ are methyl. In some embodiments, the ultravioletlight absorbing polymerizable compounds do not contain phenolic moietieswithin their structure and are therefore have less of a detrimentaleffect on polymerization rates as compared to oMTP or other phenolicultraviolet light absorbing compounds.

In some embodiments, the polymerizable composition includes a singlecomponent polymerizable methine or polymerizable anthraquinone compoundthat absorbs UV light having a wavelength from 350 nm to 400 nm and alsoabsorbs the blue-violet light with wavelengths less than about 425 nm orby mixing a co-polymerizable methine UV absorber having a wavelength ofmaximum absorption of less than about 380 nm and a co-polymerizableyellow compound having a wavelength of maximum absorption of between 380nm and 425 nm to achieve the desired absorption.

In some embodiments, the polymerizable composition contains othermonomers that contain ethylenically-unsaturated polymerizable group. Anymonomers that will polymerize with the compounds of the presentinvention can be used, including but not limited to hydrogel-formingpolymers as well as vinyl-containing monomers such as acrylic, acrylateand/or methacrylate-based monomers. Examples of monomers used in someembodiments include but are not limited to: acrylic acid, methacrylicacid and their anhydrides; crotonic acid; crotonate esters; itaconicacid as well as its anhydride; cyanoacrylic acid as well as its esters;esters of acrylic and methacrylic acids such as allyl, methyl, ethyl,n-propyl, isopropyl, butyl, tetrahydrofurfuryl, cyclohexyl, isobornyl,n-hexyl, n-octyl, isooctyl, 2-ethylhexyl, lauryl, stearyl, and benzylacrylate and methacrylate; hydroxyethyl acrylate and methacrylate;diacrylate and dimethacrylate esters of ethylene and propylene glycols,1,3-butylene glycol, 1,4-butanediol, diethylene and dipropylene glycols,triethylene and tripropylene glycols, 1,6-hexanediol, neopentyl glycol,polyethylene glycol, and polypropylene glycol, ethoxylated bisphenol A,ethoxylated and propoxylated neopentyl glycol; triacrylate andtrimethacrylate esters of tris-(2-hydroxyethyl)isocyanurate,trimethylolpropane, ethoxylated and propoxylated trimethylolpropane,pentaerythritol, glycerol, ethoxylated and propoxylated glycerol;tetraacrylate and tetramethacrylate esters of pentaerythritol andethoxylated and propoxylated pentaerythritol; acrylonitrile; vinylacetate; vinyl toluene; styrene; N-vinyl pyrrolidinone;alpha-methylstyrene; maleate/fumarate esters; maleic/fumaric acid; 1,6hexanediol di(meth)acrylate; neopentyl glycol diacrylate; methacrylate;vinyl ethers; divinyl ethers such as diethyleneglycol divinyl ether,1,6-hexanediol divinyl ether, cyclohexanedimethanol divinyl ether,1,4-butanediol divinyl ether, triethyleneglycol divinyl ether,trimethylolpropane divinyl ether, and neopentyl glycol divinyl ether,vinyl esters; divinyl esters such as divinyl adipate, divinyl succinate,divinyl glutarate, divinyl 1,4-cyclohexanedicarboxylate, divinyl1,3-cyclohexanedicarboxylate, divinyl isophthalate, and divinylterephthalate; N-vinyl pyrrolidone; tetraethylene glycol dimethacrylate;allyl acrylate; allyl methacrylate; trifunctional acrylates;trifunctional methacrylates; tetrafunctional acrylates; tetrafunctionalmethacrylates; benzyl acrylate; benzyl methacrylate; phenyl acrylate;phenyl methacrylate, phenoxyalkyl acrylates, phenoxyalkyl methacrylates,phenylalkyl acrylates; phenylalkyl methacrylates; carbazole acrylates;carbazole methacrylates; biphenyl acrylates; biphenyl methacrylates;naphthyl acrylates; naphthyl methacrylates; hydroxyalkyl acrylates andhydroxyalkyl methacrylates, such as 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropylmethacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate,2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate and thelike; acrylamide; N-alkyl acrylamides such as N-methyl acrylamide,N-ethyl acrylamide, N-propyl acrylamide, N-butyl acrylamide and thelike; acrylic acid; methacrylic acid; hydroxyethylmethacrylate;2-phenylpropyl acrylate, 2-phenylpropyl methacrylate, N-hexyl acrylate,ethylene glycol dimethacrylate; ethyl methacrylate;N,N-dimethylacrylamide and combinations of one or more of any of theforegoing. One or more additional dye compound monomers are alsoincluded in the reaction in some embodiments. By “combinations” it ismeant that combinations of two, three, four, or any other number ofmonomers are within the scope of the present invention. In someembodiments, the compounds are combined with a prepolymer formed fromone or more monomers and combined in a chain extension reaction. In someembodiments, the dye compound is formed into a prepolymer, either aloneor with one or more other monomers, then chain extended. In someembodiments, all monomers are combined together for a single reaction.All combinations of reactants and polymerization and chain extensionsteps are within the present invention.

In some embodiments, other monomers include: methyl methacrylate,2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropylacrylate, 3-hydroxypropyl methacrylate, n-vinyl pyrrolidone, styrene,eugenol (4-hydroxyvinyl benzene), .alpha.-methyl styrene. In addition,for high-refractive index foldable lens applications, suitable monomersinclude, but am not limited to: 2-ethylphenoxy methacrylate,2-ethylphenoxy acrylate, 2-ethylthiophenyl methacrylate,2-ethylthiophenyl acrylate, 2-ethylaminophenyl methacrylate, phenylmethacrylate, benzyl methacrylate, 2-phenylethyl methacrylate,3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 4-methylphenylmethacrylate, 4-methylbenzyl methacrylate, 2-2-methylphenylethylmethacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethylmethacrylate, 2-(4-propylphenyl)ethyl methacrylate;2-(4-(1-methylethyl)phenyl ethyl methacrylate, 2-(4-methoxyphenyl)ethylmethacrylate, 2-(4-cyclohexylphenyl)ethyl methacrylate,2-(2-chlorophenyl)ethyl methacrylate, 2-(3-chlorophenyl)ethylmethacrylate, 2-(4-chlorophenyl)ethyl methacrylate,2-(4-bromophenyl)ethyl methacrylate, 2-(3-phenylphenyl)ethylmethacrylate, 2-(4-phenylphenyl)ethyl methacrylate),2-(4-benzylphenyl)ethyl methacrylate, and the like, including thecorresponding methacrylates, acrylates or combinations thereof. In someembodiments, N-vinyl pyrrolidone, styrene, eugenol and G-methyl styreneare also used for high-refractive index foldable lens applications. Insome embodiments, the monomers are a combination of 2-phenylethylmethacrylate (PEMA) and 2-phenylethyl acrylate (PEA).

In some embodiments, the polymerizable composition includescopolymerizable cross-linking agent, such as a terminally ethylenicallyunsaturated compound having more than one ethylenically-unsaturatedpolymerizable group. Suitable cross-linking agents include but are notlimited to: ethylene glycol dimethacrylate, diethylene glycoldimethacrylate, allyl methacrylate, 1,3-propanediol dimethacrylate,allyl methacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanedioldimethacrylate, and 1,4-butanediol diacrylate (BDDA). Suitablecrosslinkers also include polymeric crosslinkers, such as, for example,Polyethylene glycol 1000 Diacrylate, Polyethylene glycol 1000Dimethacrylate, Polyethylene glycol 600 Dimthacrylate, Polybutanediol2000 Dimethacrylate, Polypropylene glycol 1000 Diacrylate, Polypropyleneglycol 1000 Dimethacrylate, Polytetramethylene glycol 2000Dimethacrylate, and Polytetramethylene glycol 2000 Diacrylate.

In some embodiments, the polymerizable composition includes one or morethermal free radical initiators. Examples of such initiators include,but are not limited to peroxides, such as benzoyl peroxide,peroxycarbonates, such as bis-(4-tert-butylcyclohexyl)peroxydicarbonate(PERK), azonitriles, such as azo-bis-(isobutyronitrile) (AIBN), and thelike.

In some embodiments, the methine chromophores and/or anthraquinonechromophores having ethylenically-unsaturated polymerizable groups mayundergo addition reaction to silicone having hydrosilyl groups, theaddition reaction using a catalyst such as platinum can provide asilicone compounds having a very little fear of elution of the dyedirectly bound to the silicone. Examples of the above silicone compoundshaving hydrosilyl groups are dimethylsiloxane-methylhydrosiloxanecopolymer, diphenylsiloxane-phenylhydrosiloxane copolymer,polyethylhydrosiloxane, methylhydrosiloxane-phenylmethylsiloxanecopolymer, methylhydrosiloxane-octylmethylsiloxane copolymer, methylsilicone resin containing hydrosilyl groups,polyphenyl(dimethylhydrosiloxy)siloxane and the like, but these are notlimited. Catalysts using in the addition reaction of the methinechromophores and/or anthraquinone chromophores havingethylenically-unsaturated polymerizable groups to silicone compounds aredesirably platinum compounds such as hydrogen chloroplatinate,platinum-divinyltetramethyldisiloxane, andplatinum-tetramethyltetravinylcyclosiloxane. Further, a silicone boundto the methine chromophores and/or anthraquinone chromophores havingethylenically-unsaturated polymerizable groups obtained by the abovemethod provides a silicone elastomer chemically bound to the methinechromophores and/or anthraquinone chromophores by crosslinking with asilicone having vinyl groups. Further, a silicone bound to the abovemethine chromophores and/or anthraquinone chromophores provides asilicone elastomer chemically bound to the methine chromophores and/oranthraquinone chromophores by crosslinking with a mixture of siliconehaving vinyl groups and silica. To form the above elastomer, catalystssuch as platinum compounds such as hydrogen chloroplatinate, aplatinum-divinyltetramethyldisiloxane complex, aplatinum-tetramethyltetravinylcyclotetrasiloxane complex and aplatinum-alumina supporting catalyst can be used, and such catalystsprovide a smooth crosslinking reaction. The methine chromophores and/oranthraquinone chromophores having ethylenically-unsaturatedpolymerizable groups of the present invention can be chemically bound tosilicone having hydrosylil groups and then crosslinked with siliconehaving vinyl groups. The other method is that the methine chromophoresand/or anthraquinone chromophores having ethylenically-unsaturatedpolymerizable groups of the present invention is mixed with siliconehaving hydrosilyl groups or silicone having vinyl groups, and themixture is mixed with silicone having hydrosilyl groups and siliconehaving vinyl groups, and then the mixture is cross-linked at the sametime the methine chromophores and/or anthraquinone chromophores havingethylenically-unsaturated polymerizable groups is reacted to thehydrosilyl groups. At the mixing with silicone described above, it ispreferable to homogeneously disperse the methine chromophores and/oranthraquinone chromophores having ethylenically-unsaturatedpolymerizable groups by using an appropriate solvent. As such solvents,acetone, ethanol, methanol, tetrahydrofuran, dichloromethane can beexemplified. To the solvent, the methine chromophores and/oranthraquinone chromophores having ethylenically-unsaturatedpolymerizable groups is dissolved and mixed with silicone. Then, thesolvent is distilled away with an evaporator, and the methinechromophores and/or anthraquinone chromophores havingethylenically-unsaturated polymerizable groups can be uniformlydispersed in silicone.

The foregoing are simply examples of components that may be inpolymerizable compositions and other compositions of the presentinvention. Every effective combination of two or more of the foregoingcomponents is within the present invention. Furthermore, the foregoingexamples are not intended to be limited, and any desirable or acceptablecomponent can be included in the compositions of the present invention.

Polymers and Polymerization Processes

The invention further provides compositions comprising the polymers ofthe present invention. Such compositions may contain any other suitablecomponent. In some embodiments, the composition includes both one ormore polymer(s) of the present invention and one or more light absorbingcompound(s) of the present invention. In some embodiments, the compoundsare polymerized essentially alone to form polymers formed form monomericcompounds. In some embodiments, the compounds are polymerized along withother monomers.

The polymers contain the residues of free radical polymerizationreaction of compounds and other monomers. Any method of free radicalpolymerization reaction is within the present invention. In addition,the product resulting from polymerization of any of the polymerizablecompositions of the present invention, including each combinationdisclosed above, are also included. Any polymer containing a residue ofthe free radical polymerization of a compound of the present inventionis within the present invention.

The polymerization methods of this invention include all effectivepolymerization methods including but not limited to free radical,anionic, cationic and living polymerization.

Mixtures are prepared of lens-forming monomers, ultraviolet lightabsorbing methine compounds and/or violet-blue light blocking (yellow)methine and/or violet-blue light blocking (yellow) anthraquinonemonomers in the desired proportions together with a conventional thermalfree-radical initiator. The mixture can then be introduced into a moldof suitable shape to form the lens, and the polymerization carded out bygentle heating to activate the initiator. Examples of thermal freeradical initiators include, but are not limited to peroxides, such asbenzoyl peroxide, peroxycarbonates, such asbis-(4-tert-butylcyclohexyl)peroxydicarbonate (PERK), azonitriles, suchas azo-bis-(isobutyronitrile) (AIBN), and the like.

In some embodiments, the monomers are photopolymerized by using a moldwhich is transparent to actinic radiation of a wavelength capable ofinitiating polymerization of these acrylic monomers by itself.Conventional photoinitiator compounds, e.g., a benzophenone-typephotoinitiator, are optionally introduced to facilitate thepolymerization. Photosensitizers can be introduced as well to permit theuse of longer wavelengths. In some embodiments of polymers intended forlong residence within the eye, the number of ingredients in the polymeris minimized to decrease the risk of having materials leach from thelens into the interior of the eye.

In some embodiments, these monomers are cured directly in apolypropylene mold so that a finished optic is produced. The time andtemperature for curing vary with the particular lens-forming materialchosen. The optic may be combined in a number of known ways with avariety of known optics to produce an IOL.

Articles

The invention also provides articles that contain the compounds of thepresent invention, the polymers of the present invention, thecompositions of the present invention, or a combination thereof of thepresent invention. In some embodiments, an entire article is made of oneor more compounds, polymers, or compositions of the present invention.In some embodiments, an entire article is made of a mixture, solution,or other combination that includes one or more compound, polymer, orcompositions of the present invention. In some embodiments, a componentof the article is made is made of one or more compounds, polymers, orcompositions of the present invention. In some embodiments, a componentof the article is made is made of a mixture, solution, or othercombination that includes one or more compound, polymer, or compositionsof the present invention. Articles that include more than one compound,polymer, composition, or combination thereof of are also within thepresent invention.

In some embodiments, the article is or includes a component that istransparent or otherwise permeable to certain wavelengths of visiblelight. In some embodiments, the article is an optic lens such as lensesuseful in windows, contact lenses, telescopes, eyeglasses or sunglasses.In some embodiments, the article is an ocular lens used as an IOL.

In some embodiments, the articles include coatings that containcompounds of the present invention. Such coatings are produced by anymeans, including but not limited to casting, spin casting, dipping,immersion, or spraying.

In some embodiments, the compounds or polymers are applied in a liquidcarrier such as a solvent. After coating, the carrier is removed (forexample, by evaporation of the solvent) leaving the compound or polymeron the coated substrate. In some embodiments, the coating is present asa yellow film and/or a UV absorbing film onto a substrate.

Methods of making the articles of the present invention are also withinthe present invention. In some embodiments, one or more of thepolymerizable compounds of this invention are dissolved into a suitablemonomer formula, cast onto a substrate (e.g. a transparent material) andcured by a suitable free-radical initiation procedure, such as exposureto heat or UV radiation.

In some embodiments, the compounds of this invention are dissolved intoa suitable solvent or monomer formula, followed by immersion of anarticle or material into the solution containing the compound. Thesolution enters the polymer (for example, by absorption) then thepolymer is dried. The result is incorporation into the matrix of thepolymer. The polymerizable compounds are then cured, for example byheat, radiation or other means suitable to bond the compound into thepolymer.

This invention can be further illustrated by the following examples,although it will be understood that these examples are included merelyfor purposes of illustration and are not intended to limit the scope ofthe invention.

EXAMPLES

Examples 1 through 103 are prophetic examples of some of the compoundsthat are within the present invention. These examples use Formulas IIthrough VI to describe compound by identifying the various groups inFormulas II through VI. Examples 1 through 94 each identify onecompound, Examples 1 through 52 identify compounds using Formula II.Examples 53 through 78 identify compounds using Formula III. ForExamples 1 through 78, in cases where numbers are provided along withthe identity of the R₂ groups in the tables, those numbers indicate theposition on the ring in the diagram of Formula II or Formula IV, asapplicable. Examples 79 through 94 identify compounds using Formula III.Examples 95 through 103 each identify two compounds because eachidentify groups (L and Q) that appear (in different locations) on themolecule described in both Formula V and Formula VI. These examplesfollow, with the formulas provided for reference, each at the beginningof group of Examples to which they apply.

II

Ex- am- ple Num- ber R R₁ R₂ X₁ X₂  1 —CH₂CH₃ —CH₂CH₃ —H —CN—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂  2 —CH₃ —CH₃ —H —CN—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂  3 —CH₃ —CH₂CH₂—CN —H —CN—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂  4 —CH₂CH₂CN —CH₂C₆H₅ 2-CH₃ —CN—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂  5 —CH₂CH₂—CN —CH₂CH₂—C₆H₅ —H —CN—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂  6

—H —CN —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂  7 —CH₂C₆H₅ —CH₂C₆H₅ —H —CN—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂  8 —CH₂CH₃ —CH₂CH₃ —H

 9 —CH₃ —CH₃ —H

10 —CH₃ —CH₂CH₂—CN —H —CN

11 —CH₃ —CH₂C₆H₅ —H —CN

12 —CH₂CH₂—CN —CH₂CH₂—OC(O)CH₃ —H —CN

13 —(CH₂CH₂O)₃₋₁₀C(O)C(CH₃)═CH₂ —(CH₂CH₂O)₃₋₁₀C(O)C(CH₃)═CH₂ —H

—CO₂CH₃ 14 —CH₃ —(CH₂CH₂O)₃₋₁₀C(O)C(CH₃)═CH₂ —H —CO₂CH₃ —CONH₂ 15—(CH₂CH₂O)—C(O)C(CH₃)═CH₂ —(CH₂CH₂O)—C(O)C(CH₃)═CH₂ —H —CO₂CH₃ —CONH₂ 16—(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —H —CONH₂—CONH₂ 17 —CH₃ —COC(CH₃)═CH₂ H —CO₂CH₃ —CO₂CH₃ 18 —CH₃

H —CO₂CH₃ —CO₂CH₃ 19 —CH₃ —COC(CH₃)═CH₂ —H —CN —CN 20 R & R₁ arecombined

—H —CN

21 R & R₁ are combined

—H —CN

22 R & R₁ are combined

—H —CN —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 23 R & R₁ are combined

—H —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 24 R &R₁ are combined

—H

25 R & R₁ are combined

—H

—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 26 R & R₁ are combined

—H —C₆H₅ —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 27 R & R₁ are combined

—H —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 28 R &R₁ are combined

—H

29 —(CH₂CH₂O)—C(O)C(CH₃)═CH₂ —(CH₂CH₂O)—C(O)C(CH₃)═CH₂ —H

30 —(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —H

31 —CH₃ —COC(CH₃)═CH₂ —H

32 —CH₃

—H

33 —CH₃ —(CH₂CH₂O)—C(O)C(CH₃)═CH₂ —H —C₆H₅ —CN 34 —CH₃—(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —H —C₆H₅ —CN 35 —CH₃

—H —C₆H₅ —CN 36 —CH₃

—H —CN —CN 37 —CH₃

—H —CO₂CH₃ —CO₂CH₃ 38 —CH₂CH₃ —C₆H₁₁ 2-Cl

39 —CH₂CH₃ —C₆H₁₁ 2-Cl —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 40 —CH₂CH₂Cl —C₂H₅ 2-CH₃

41 —CH₂CH₂CN —C₂H₅ 2-CH₃ —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 42 R & R₁ are combined

—H —CN —CONH—CH₂CH(CH₃)—OCOCH═CH₂ 43 R & R₁ are combined

—H —CN —CONH—CH₂CH₂—OCOCH═CH₂ 44 —CH₃ —COCH═CH₂ —H

45 R & R₁ are combined

—H —CN —CONH—CH₂C(CH₃)₂CH₂OCOC(CH₃)═CH₂ 46 —CH₂CH₂CN —CH₂CH₂Cl —H —CN—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 47 —CH₂CH₂CN

—H —CN —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 48 —CH₂CH₂CN

—H —CN —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 49 —CH₂CH₂CN

—H —CN —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 50 —CH₂CH₂CN

—H —CN —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 51 —CH₂CH₂CN

—H —CN —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 52 —CH₂CH₂CN

—H —CN

III

Example Number R₂ R₃ X₁ X₂ 53 —H —H —CN —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂54 —H —CH₃ —CN —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 55 —3-OCH₃ —COC(CH₃)═CH₂—CN —NH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 56 —3-OCH₃ —COC(CH₃)═CH₂ —CN —CO₂C₂H₅57 —3-OCH₃ —(CH₂CH₂O)—C(O)C(CH₃)═CH₂ —CN —CN 58 —3-OCH₃—(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —CN —C₆H₅ 59 —3-OCH₃—(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —CN

60 —3-OCH₃ —(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —CN

61 —3-OCH₃ —(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —CN

62 —H —COC(CH₃)═CH₂ —CN —CO₂C₄H₉-n 63 —H —(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂—CN —CN 64 —H —(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —CN —C₆H₅ 65 —H—(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —CN

66 —H —(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —CO₂C₂H₅ —CO₂C₂H₅ 67 —H —CH₃ —CN—CONH(CH₂CH₂O)₆₋₁₀—(CH₂CH(CH₃)O)₆₋₁₀COC(CH₃)═CH₂ 68 —H—(CH₂CH₂O)₃₋₂₀—C(O)C(CH₃)═CH₂ —CN —CO₂CH₃ 69 —3-OCH₃ —CH₃ —CN—NH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 70 —3-OCH₃ —CH₃ —CN—NH—CH₂CH₂—OCOC(CH₃)═CH₂ 71 —3-OCH₃ —CH₃ —CN

72 —3-OCH₃ —CH₃ —CN

73 —3-OCH₃ —CH₃

74 —3-Br —(CH₂CH(CH₃)O)—C(O)C(CH₃)═CH₂ —CN

75 —3-OCH₃ —COC(CH₃)═CH₂ —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 76 —3-OCH₃ —CH₂C₆H₅—CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ —CONH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 77 —H—CH₂C₆H₅ —CN —CONH—CH₂CH₂O—CH₂CH₂—OCOC(CH₃)═CH₂ 78 —3-OCH₃ H —CN—CONH—CH₂C(CH₃)₂CH₂OCOC(CH₃)═CH₂

IV

Example Number X₁ Y 79 —CN —NH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 80 —CN—NH—CH₂CH(CH₃)—OCOCH═CH₂ 81 —CN —NH—CH₂CH₂—OCOC(CH₃)═CH₂ 82 —CN

83 —CN

83 —C(O)CH₃ —NH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 85

—NH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 86

—NH—CH₂CH₂—OCOC(CH₃)═CH₂ 87 —C(O)CH₃

88

89 —C(O)C(CH₃)₃ —NH—CH₂C(CH₃)₂CH₂OCOC(CH₃)═CH₂ 90

—NH—CH₂CH(CH₃)—OCOC(CH₃)═CH₂ 91 —CN

92 —CN

93 —C(O)C(CH₃)₃

94

—O—(CH₂CH₂O)₆₋₁₀—(CH₂CH(CH₃)O)₆₋₁₀COC(CH₃)═CH₂

V

VI

Example L—Q  95 —CH₂CH(CH₃)—OCOC(CH₃)═CH₂  96 —CH₂CH₂—OCOC(CH₃)═CH₂  97—CH₂CH₂—OCOCH═CH₂  98

 99 —(CH₂CH₂O)₆₋₁₀—(CH₂CH(CH₃)O)₆₋₁₀COC(CH₃)═CH₂ 100—(CH₂)₁₀O—COC(CH₃)═CH₂ 101 —(CH₂CH₂O)₁₀₋₁₀₀—COC(CH₃)═CH₂ 102—(CH₂CH₂O)₂₋₅—COC(CH₃)═CH₂ 103 —(CH₂C(CH₃)₂CH₂O)—COCH═CH₂

Examples 104 through 132 describe actual procedures that were performedin preparing some of the compounds of the present invention and theirprecursors. Each of Examples 104 through 132 includes a drawing to showthe reaction and its product. Stereochemistry of the products of thesereactions was not determined, so the diagrams in Examples 104 through132 should not be interpreted as distinguishing the cis or transstereoisomer.

Examples 133 through 136 describe examples of some of the procedures forpreparing a polymer and polymerizing compounds.

Example 104

To a clean, dry 1 L 4-neck flask equipped with a mechanical stirrer,heating mantle, thermocouple, addition funnel and a Dean-Stark trap wereadded 99 g of methyl cyanoacetate (1.0 mol). The reaction vessel wasstirred under an atmosphere of dry nitrogen and heated to 95° C. To thereaction vessel were added 61.1 g (1.0 mol) of ethanolamine at adropwise rate while removing low boilers via the Dean-Stark trap. Anexotherm occurred early during the addition and the temperatureincreased to 105° C. The addition was complete in about 45 minutes andthe reaction vessel temperature was increased to 150° C. After about 1 hlow boilers were no longer being collected in the Dean-Stark trap. Thereaction solution was allowed to cool to about 85° C. and 125 mL ofcyclohexane was added at a rapid, dropwise rate. The cyclohexane wasdecanted. A fresh 75 mL of cyclohexane were added and the warm mixturewas transferred to a 600 mL beaker. The product began to solidify togive a waxy solid. The solid was broken upon as much as possible using aspatula and the cyclohexane was decanted. The solid was transferred to aCoors dish and place in the chemical hood to dry overnight. Upon dryingthe solid had a mass of 120.8 g.

Example 105

To a clean, dry 500 mL flask equipped with a heating mantle and additionfunnel were added 200 mL of DMF and 50.7 g ofN-phenylthiomorpholine-S,S-dioxide (0.2 mol, available from EastmanChemical Company). The reaction vessel was purged with nitrogen and 20.5mL of phosphorus oxychloride (0.2 mol) were added at such a rate to keepthe temperature from exceeding 35° C. The reaction vessel was heated to80-90° C. and stirred for about 4 h. The reaction mixture was allowed tocool to room temperature and poured into a mechanically stirred icewater mixture (1 L) containing 100 mL of concentrated ammoniumhydroxide. A white precipitate formed that was collected by suctionfiltration and washed with water. The cake was allowed to dry on thefilter overnight to give 54.4 g of product.

Example 106

To a 500 mL round-bottomed flask equipped with a mechanical stirrer,reflux condenser and heating mantle were added methanol (175 mL), 18.0 gof product from Example 105 (75.0 mmols) and 10.4 g of product fromExample 104 (80.0 mmols). The mixture was heated to reflux and stirredfor 3 h then allowed to cool to room temperature, at which time aprecipitate formed. The precipitate was collected by suction filtration,washed with cold methanol and allowed to dry on the filter overnight togive 19.75 g of light yellow compound.

Example 107

To a clean, dry 50 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 20 mL of acetone, 4.0 g ofproduct from Example 106 (11.4 mmols), 4.3 mL of methacrylic anhydride(28.6 mmols), 4.0 mL of triethylamine (28.6 mmols), 70 mg of4-dimethylaminopyridine (DMAP, 0.6 mmol) and 40 mg of hydroquinone. Thereaction mixture was heated to 50° C. with stirring for about 30minutes, at which time the starting material was consumed according toTLC analysis (TLC; 1:1 tetrahydrofuran/cyclohexane; Rf (product fromExample 106)=0.06; Rf (product from Example 107)=0.32). Upon reactioncompletion, a precipitate formed. The reaction mixture was allowed tocool to about 30° C. and 20 mL of methanol were added at a dropwiserate. The solid precipitate was collected by suction filtration andwashed twice with 20 mL of methanol. The cake was allowed to dry on thefilter overnight to give 2.58 g of free flowing yellow powder. Theidentity of the product was determined to be the target compound byHPLC-MS and the purity was estimated to be about 98%. The compoundexhibited a wavelength of maximum absorption (λ_(max)) at 374.19 nm anda molar absorptivity (c) of 25,900, as determined by Ultraviolet-Visiblelight spectroscopy (UV-Vis) in N,N-dimethylformamide (DMF) solvent.

Example 108

To a clean, dry 500 mL 4-neck flask equipped with a mechanical stirrer,heating mantle, thermocouple and a Dean-Stark trap were added 75 g ofmethyl cyanoacetate (0.75 mol). The reaction vessel was stirred under anatmosphere of dry nitrogen and heated to 95° C. To the reaction vesselwere added 58 mL of 1-amino-2-propanol at a dropwise rate while removinglow boilers via the Dean-Stark trap. Once the addition was complete, thereaction vessel temperature was increased to 150° C. After about 1 h,low boilers were no longer being collected in the Dean-Stark trap. Thereaction solution was allowed to cool to about 50° C. and transferred toa storage vessel to give 103.1 g of an oil that solidified uponstanding.

Example 109

To a 500 mL round-bottomed flask equipped with a mechanical stirrer,reflux condenser and heating mantle were added methanol (100 mL), 9.0 gof product from Example 105 (37.5 mmols) and 5.7 g of product fromExample 108 (40.0 mols). The mixture was heated to reflux and stirredfor 3 h then allowed to cool to about 10° C. using an ice-water bath tocrystallize the compound. The crystals were collected by suctionfiltration, washed with cold water and allowed to dry on the filterovernight to give 8.72 g of light yellow compound. The identity of theproduct was determined to be the target compound by HPLC-MS and thepurity was estimated to be about 88%. The compound exhibited awavelength of maximum absorption (λ_(max)) at 370.88 nm and a molarabsorptivity (c) of 24,600 as determined by Ultraviolet-Visible lightspectroscopy (UV-Vis) in DMF solvent.

Example 110

To a 100 mL round bottomed flask equipped with a magnetic stirrer andheating mantle were added 20 mL of DMF, 1.28 g of3-isopropenyl-α,α′-dimethylbenzylisocyanate (6 mmols), 2.18 g of productfrom Example 109 (6 mmols) and 3 drops of dibutyltin dilaurate. Thereaction mixture was heated to 90° C. After about 2 h another 10 dropsof 3-isopropenyl-α,α′-dimethylbenzylisocyanate were added since TLCanalysis revealed that the reaction had not gone to completion. Thereaction mixture was allowed to stir for another 2 h at 90° C. thenallowed to cool to room temperature. The product compound wasprecipitated by drowning the reaction mixture, with stirring, into 60 mLof a 50 volume percent solution of methanol and aqueous sodium chloride(10 weight percent). The solid was collected by suction filtration andwashed with a 50 volume percent solution of methanol and aqueous sodiumchloride (10 weight percent). After drying on the filter overnight, theprecipitate had a mass of 0.66 g. The product was determined to be acomponent of the solid material by HPLC-MS and the purity was estimatedto be about 40%. The compound exhibited a wavelength of maximumabsorption (λ_(max)) at 388 nm as determined by Ultraviolet-Visiblelight spectroscopy (UV-Vis) in DMF solvent.

Example 111

To a clean, dry 100 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 25 mL of anhydrous ethanol, 4.0g of product from Example 104 (31.2 mmols), 4.43 g of4-N,N-dimethylaminobenzaldehyde (29.7 mmols) and 4 drops of a 25 weightpercent solution of sodium methoxide in methanol. The reaction mixturewas heated to reflux with stirring until the4-N,N-dimethylaminobenzaldehyde had be consumed according to TLCanalysis (TLC; 1:1 tetrahydrofuran/cyclohexane; R_(f) (product fromExample 111)=0.20). Upon reaction completion the reaction solution wasallowed to cool to room temperature and stir overnight. A precipitateformed. The precipitate was collected by suction filtration and washedwith about 25 mL of methanol. The cake was allowed to dry on the filterovernight to give 2.87 g of free flowing yellow powder. The identity ofthe product was determine to be the target compound by HPLC-MS and thepurity was estimated to be about 96%. The compound exhibited awavelength of maximum absorption (λ_(max)) at 422 nm as determined byUltraviolet-Visible light spectroscopy (UV-Vis) in DMF solvent.

Example 112

To a clean, dry 50 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 10 mL of acetone, 1.0 g ofproduct from Example 111 (3.86 mmols), 0.72 mL of methacrylic anhydride(4.82 mmols), 0.67 mL of triethylamine (4.82 mmols), 23.6 mg of4-dimethylaminopyridine (DMAP, 0.19 mmols) and 10 mg of hydroquinone.The reaction mixture was heated to 50° C. with stirring for about 35minutes, at which time the starting material was consumed according toTLC analysis (TLC; 1:1 tetrahydrofuran/cyclohexane; Rf (product fromExample 111)=0.19; Rf (product from Example 112)=0.50). The reactionmixture was allowed to cool to room temperature and product from Example112 was precipitated by adding 12 mL of a 5:1 solution of water inmethanol at a dropwise rate while stirring. The solid precipitate wascollected by suction filtration and washed with 6.0 mL of a 5:1 solutionof water in methanol. The cake was allowed to dry on the filterovernight to give 1.26 g of free flowing yellow powder. The identity ofthe product was determined to be the target compound by HPLC-MS and thepurity was estimated to be about 93%. The compound exhibited awavelength of maximum absorption (λ_(max)) at 392.08 nm and a molarabsorptivity (c) of 28,800 as determined by Ultraviolet-Visible lightspectroscopy (UV-Vis) in DMF solvent.

Example 113

Part I.

To a clean, dry 500 mL flask equipped with a heating mantle and additionfunnel were added 50 mL of DMF and 16.0 g ofN-methyl-N-2-cyanoethylaniline (0.1 mol). The reaction vessel was purgedwith nitrogen and 10.0 mL of phosphorus oxychloride (0.2 mols) wereadded at such a rate to keep the temperature from exceeding 35° C. Thetemperature was regulated using an ice water bath. The reaction vesselwas heated to 80-90° C. and stirring for about 2 h. The reaction mixturewas allowed to cool to about 40° C.

Part II.

A portion of the product from Example 104 (12.8 g, 0.1 mol) wasdissolved into 200 mL of isopropyl alcohol in a 1 L beaker. Anhydroussodium acetate (40.0 g) was added to the beaker, the mixture was stirredand the beaker was heated to 75° C. To this mixture was added thereaction mixture from Part I (Vilsmeier complex) at a fairly rapid rate.When the addition was complete, the reaction mixture was stirred for anadditional 1 h and allowed to cool to room temperature. The reactionmixture was added at a rapid dropwise rate to 400 mL of an ice watersolution. The dark mixture was transferred to a 4 L beaker equipped witha mechanical stirrer and stirred. Water (350 mL) was added at a dropwiserate and the solution became cloudy. Another 400 mL of water were addedwith stirring and the compound began to precipitate. The precipitate wascollected by suction filtration and washed with cold water followed bywarm water. The cake was allowed to dry on the filter overnight to give17.5 g of compound. The identity of the product was determined to be thetarget compound by HPLC-MS and the purity was estimated to be about 95%.The compound exhibited a wavelength of maximum absorption (λ_(max)) at381.8 nm and a molar absorptivity (c) of 27,000 as determined byUltraviolet-Visible light spectroscopy (UV-Vis) in DMF solvent.

Example 114

To a clean, dry 50 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 50 mL of acetone, 3.5 g ofproduct from Example 113 (11.7 mmols), 2.5 mL of methacrylic anhydride(16.8 mmols), 2.0 mL of triethylamine (16.8 mmols), 70 mg of4-dimethylaminopyridine (DMAP, 0.6 mmlos) and 30 mg of hydroquinone. Thereaction mixture was heated to 50-55° C. with stirring for about 45minutes, at which time the starting material had not been consumedaccording to TLC analysis (TLC; 1:1 tetrahydrofuran/cyclohexane).Another 10 drops of methacrylic anhydride were added to the reactionmixture. The reaction mixture was stirred for an additional 30 minutesthen allowed to cool to room temperature and the product wasprecipitated by adding about 50 mL of a 5:1 solution of water inmethanol at a dropwise rate while stirring. The solid precipitate wascollected by suction filtration and washed with water. The cake wasallowed to dry on the filter overnight to give 3.43 g of yellow powder.The identity of the product was determined to be the target compound byHPLC-MS and the purity was estimated to be about 92%. The compoundexhibited a wavelength of maximum absorption (λ_(max)) at 381.8 nm and amolar absorptivity (c) of 28,300 as determined by Ultraviolet-Visiblelight spectroscopy (UV-Vis) in DMF solvent.

Example 115

To a 500 mL round bottomed flask equipped with a magnetic stirrer,thermocouple and heating mantle were added 24 g of1,8-dihydroxyanthraquinone (0.1 mole), 88 g of ethylene carbonate (1.0mole), 0.5 g of tetramethylammonium chloride and 75 mL of ethyleneglycol. The reaction mixture was heated to 150° C. for 20 h. TLCanalysis revealed that the starting material had been consumed. Thereaction mixture was allowed to cool to about 80° C. and the product wasprecipitated by adding 500 mL of warm water with stirring. The solid wascollected by suction filtration, washed with hot water and allowed todry on the filter overnight to give 21.0 g of a tacky solid. The solidmaterial was broken up and added to a 2 L beaker containing toluene. Themixture was heated to boiling while constantly stirring. The mixture wasallowed to cool to about 80° C. and filtered. The solid was collectedand washed with toluene and allowed to dry on the filter overnight togive 16.8 g of product. The identity of the product was determined to bethe target compound by HPLC-MS and the purity was estimated to be about85%. An ethylenically-unsaturated polymerizable group can be readilyattached to the hydroxyethyl groups on the product by any effectivemeans, for example by reaction with an appropriate anhydride such asmethacrylic anhydride as in Example 114.

Example 116

To a clean, dry 100 mL round bottomed flask equipped with a magneticstirrer were added 20 mL of DMF, 10.0 g of ethyl2-cyano-3-(hydroxyphenyl)propenoate (46.1 mmols, for preparation seeU.S. Pat. No. 4,617,374, Example A), 13.7 mL of methacrylic anhydride(92.2 mmols), 12.9 mL of triethylamine (92.2 mmols), 563 mg of4-dimethylaminopyridine (DMAP, 4.6 mmlos) and 100 mg of hydroquinone.The reaction mixture was stirred at room temperature for about 18 h. Theproduct was precipitated by drowning the reaction mixture into 50 mL ofwater. The solid precipitate was collected by suction filtration andwashed with water. The cake was allowed to dry on the filter overnightto give 10.60 g of off white powder. The identity of the product wasdetermined to be the target compound by HPLC-MS and the purity wasestimated to be about 96%. The compound exhibited a wavelength ofmaximum absorption (λ_(max)) at 312 nm as determined byUltraviolet-Visible light spectroscopy (UV-Vis) in DMF solvent.

Example 117

To a 1 L flask equipped with a mechanical stirrer and heating mantlewere added 53 g of 50 weight percent aqueous sodium hydroxide (0.66 mol)and 375 mL of warm water with stirring. Vanillin (68.4 g, 0.45 mol) wasadded followed by the dropwise addition of 53 mL of 2-chloroethanol(0.54 mol) over about 1 h. During the addition of 2-chloroethanol, thereaction mixture was gradually heated to 100° C. The reaction mixturewas stirred at 100° C. for an additional 16 h and allowed to cool toroom temperature. The reaction mixture was composed of two phases thattested acidic according to pH test strips. The mixture was stirred andmade basic by adding about 5 mL of concentrated ammonium hydroxide togive a solution. The solution was poured onto about 400 g of ice thatcaused the desired product to precipitate. The precipitate was collectedby suction filtration, washed with cold water and allowed to dry on thefilter overnight to give 70.6 g of product. The solid product had amelting point range of 94-96° C. HPLC-MS analysis was used to confirmthe identity of the product and the purity was estimated to be 94%.

Example 118

To a clean, dry 500 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 150 mL of methanol, 39.2 g ofproduct from Example 117 (0.2 mols), 19.8 g of methyl cyanoacetate (0.2mols) and 5 drops of piperidine. The reaction mixture was heated toreflux with stirring for 1.5 h. Upon reaction completion the reactionsolution was allowed to cool to room temperature at which time thematerial began to precipitate. Another 50 mL of chilled methanol wereadded and the precipitate was collected by suction filtration. The cakewas washed with a small amount of chilled methanol and allowed to dry onthe filter overnight to give 49.6 g of free flowing yellow powder. Theidentity of the product was determined to be the target compound byHPLC-MS and the purity was estimated to be about 97%. The compoundexhibited a wavelength of maximum absorption (λ_(max)) at 366.8 nm and amolar absorptivity (c) of 22,400 as determined by Ultraviolet-Visiblelight spectroscopy (UV-Vis) in DMF solvent.

Example 119

To a 100 mL round bottomed flask equipped with a magnetic stirrer andheating mantle were added 25 mL of toluene, 0.8 g of3-isopropenyl-α,α′-dimethylbenzylisocyanate (4.0 mmols), 1.04 g ofmethyl 2-cyano-3-(4-hydroxyethoxy-3-methoxyphenyl)propenoate (3.75mmols, Example 118) and 3 drops of dibutyltin dilaurate. The reactionmixture was heated to 90° C. After about 45 minutes, the reaction wascomplete according to TLC analysis (1:1 THF/Cyclohexane). The reactionmixture was allowed to cool to room temperature. The product wasprecipitated by drowning the reaction mixture, with stirring, into 200mL of heptane. The yellow solid was collected by suction filtration andwashed with heptane and allowed to dry on the filter overnight to give1.5 g of product. The identity of the product was determined to be thetarget compound by HPLC-MS and the purity was estimated to be about 94%.The compound exhibited a wavelength of maximum absorption (λ_(max)) at362.0 nm as determined by Ultraviolet-Visible light spectroscopy(UV-Vis) in DMF solvent.

Example 120

To a clean, dry 1 L round bottomed flask equipped with a magneticstirrer and reflux condenser were added 200 mL of acetone, 33.2 g ofproduct from Example 118 (0.12 mol), 23.0 mL of methacrylic anhydride(0.15 mmol), 20.0 mL of triethylamine (0.14 mol), 0.7 g of4-dimethylaminopyridine (DMAP, 5.7 mmlos) and 400 mg of hydroquinone.The reaction mixture was heated to 50-55° C. with stirring for about 45minutes, at which time the starting material had not been consumedaccording to TLC analysis (TLC; 1:1 tetrahydrofuran/cyclohexane).Another 2-3 mL of methacrylic anhydride were added to the reactionmixture. The reaction mixture was stirred for an additional 30 minutesthen allowed to cool to room temperature and the product wasprecipitated by adding about 350 mL of cold water at a rapid rate whilestirring. The solid precipitate was collected by suction filtration,washed with water and washed with a small amount of cold methanol. Thecake was allowed to dry on the filter overnight to give 37.1 g of yellowpowder. The identity of the product was determined to be the targetcompound by HPLC-MS and the purity was estimated to be about 95%. Thecompound exhibited a wavelength of maximum absorption (λ_(max)) at 362.8nm and a molar absorptivity (c) of 21,800 as determined byUltraviolet-Visible light spectroscopy (UV-Vis) in DMF solvent.

Example 121

Part I.

To a clean, dry 300 mL flask equipped with a heating mantle and additionfunnel were added 40 mL of DMF and 12.5 g of3,3′-(phenylimino)dipropionitrile (0.06 mol). The reaction vessel waspurged with nitrogen and 6.5 mL of phosphorus oxychloride (0.042 mol)were added at such a rate to keep the temperature from exceeding 35° C.The temperature was regulated using an ice water bath. The reactionvessel was heated to 80-90° C. and stirred for about 1 h. The reactionmixture was allowed to cool to about 40° C.

Part II.

A portion of the product from Example 104 (7.7 g, 0.6 mol) was dissolvedinto 90 mL of absolute ethanol in a 1 L beaker. Anhydrous sodiumcarbonate (24 g) was added to the beaker, the mixture was stirred andthe beaker was heated to 75° C. To this mixture was added the mixturefrom Part I (Vilsmeier complex) at a fairly rapid rate. When theaddition was complete, the reaction mixture was stirred for anadditional 1 h at 75° C. and allowed to cool to room temperature. Thereaction mixture was added at a rapid dropwise rate to 400 mL of icewater to precipitate the product. The precipitate was collected bysuction filtration and washed with warm water. The cake was allowed todry on the filter overnight to give 13.9 g of product. The identity ofthe product was determined to be the target compound by HPLC-MS and thepurity was estimated to be about 97%. The compound exhibited awavelength of maximum absorption (λ_(max)) at 369.91 nm and a molarabsorptivity (c) of 28,400 as determined by Ultraviolet-Visible lightspectroscopy (UV-Vis) in DMF solvent.

Example 122

To a clean, dry 100 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 50 mL of acetone, 3.95 g ofproduct from Example 121 (11.7 mmols), 2.5 mL of methacrylic anhydride(16.8 mmols), 2.0 mL of triethylamine (14.3 mmols), 0.07 g of4-dimethylaminopyridine (DMAP, 0.6 mmlos) and 40 mg of hydroquinone. Thereaction mixture was heated to 50° C. with stirring for about 45minutes, at which time the starting material had been consumed accordingto TLC analysis (TLC; 75:25 tetrahydrofuran/cyclohexane). The reactionmixture was stirred for an additional 20 minutes then allowed to cool toroom temperature and the product was precipitated by adding about 50 mLof cold water at a moderate rate while stirring. The solid precipitatewas collected by suction filtration, washed with water and washed with asmall amount of a 4:1 solution of water and methanol, respectively. Thecake was allowed to dry on the filter overnight to give 3.77 g of lightyellow powder. The identity of the product was determined to be thetarget compound by HPLC-MS and the purity was estimated to be about 94%.The compound exhibited a wavelength of maximum absorption (λ_(max)) at370.9 nm and a molar absorptivity (c) of 30,100 as determined byUltraviolet-Visible light spectroscopy (UV-Vis) in DMF solvent.

Example 123

To a 100 mL round bottomed flask equipped with a magnetic stirrer andheating mantle were added 35 mL of toluene, 2.5 g of3-isopropenyl-α,α′-dimethylbenzylisocyanate (12.4 mmols), 3.4 g of theproduct from example 121 (10 mmols) and 4 drops of dibutyltin dilaurate.The reaction mixture was heated to 90-95° C. After about 2 h, thereaction was complete according to TLC analysis (72:25 THF/Cyclohexane).The reaction mixture was allowed to cool to about 65° C. and addedslowly to a moderately stirred beaker containing 50 mL of heptane toprecipitate the product. The resulting slurry was further cooled to15-20° C. using an ice-water bath. The light yellow solid was collectedby suction filtration, washed with heptane and allowed to dry on thefilter overnight to give 4.27 g of product. The identity of the productwas determined to be the target compound by HPLC-MS and the purity wasestimated to be about 79%. The compound exhibited a wavelength ofmaximum absorption (λ_(max)) at 371.26 nm and a molar absorptivity (c)of 24,600 as determined by Ultraviolet-Visible light spectroscopy(UV-Vis) in DMF solvent.

Example 124

Part I.

To a clean, dry 300 mL flask equipped with a heating mantle and additionfunnel were added 40 mL of DMF and 12.5 g of3,3′-(phenylimino)dipropionitrile (0.06 mol). The reaction vessel waspurged with nitrogen and 6.5 mL of phosphorus oxychloride were added atsuch a rate to keep the temperature from exceeding 35° C. Thetemperature was regulated using an ice water bath. The reaction vesselwas heated to 80-90° C. and stirred for about 2 h. The reaction mixturewas allowed to cool to about 40° C.

Part II.

A portion of the product from Example 108 (8.5 g, 0.6 mol) was dissolvedinto 75 mL of absolute ethanol in a 1 L beaker. Anhydrous sodium acetate(24 g) was added to the beaker, the mixture was stirred and the beakerwas heated to 75° C. To this mixture was added the mixture from Part I(Vilsmeier complex) at a fairly rapid dropwise rate. When the additionwas complete, the reaction mixture was stirred for an additional 1 h at75° C. and allowed to cool to room temperature. The reaction mixture wasadded at a rapid dropwise rate to 400 mL of ice water to precipitate theproduct. The precipitate was collected by suction filtration and washedwith cold water followed by warm water. The cake was allowed to dry onthe filter overnight to give 17.5 g of product. The identity of theproduct was determined to be the target compound by HPLC-MS and thepurity was estimated to be about 84%. The compound exhibited awavelength of maximum absorption (λ_(max)) at 371.25 nm and a molarabsorptivity (c) of 30,700 as determined by Ultraviolet-Visible lightspectroscopy (UV-Vis) in DMF solvent.

Example 125

To a clean, dry 100 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 40 mL of acetone, 3.15 g ofproduct from Example 124 (9.0 mmols), 1.8 mL of methacrylic anhydride(12.6 mmols), 1.5 mL of triethylamine (10.8 mmols), 0.05 g of4-dimethylaminopyridine (DMAP, 0.4 mmol) and 30 mg of hydroquinone. Thereaction mixture was heated to 50° C. with stirring for about 1 h. Asmall amount of Example 124 remained according to TLC analysis (TLC;75:25 tetrahydrofuran/cyclohexane). An additional 25 drops ofmethacrylic anhydride were added. The reaction mixture was stirred foran additional 2 h. TLC analysis revealed that a slight amount of Example124 remained thus another 10 drops of methacrylic anhydride were added.The reaction mixture was stirred for an additional 1 h then allowed tocool to room temperature and stir overnight. The product wasprecipitated by adding about 50 mL of cold water at a dropwise ratewhile stirring. The solid precipitate was collected by suctionfiltration, washed with water and allowed to dry on the filter overnightto give 3.15 g of light yellow powder. The identity of the product wasdetermined to be the target compound by HPLC-MS and the purity wasestimated to be about 89%. The compound exhibited a wavelength ofmaximum absorption (λ_(max)) at 371.71 nm and a molar absorptivity (c)of 30,500 as determined by Ultraviolet-Visible light spectroscopy(UV-Vis) in DMF solvent.

Example 126

To a 100 mL round bottomed flask equipped with a magnetic stirrer andheating mantle were added 50 mL of toluene, 2.5 g of3-isopropenyl-α,α′-dimethylbenzylisocyanate (12.4 mmols), 3.15 g of theproduct from example 124 (9 mmols) and 3 drops of dibutyltin dilaurate.The reaction mixture was heated to 90-95° C. After about 5 h, TLCanalysis revealed that some of Example 124 remained (72:25THF/Cyclohexane). Another 15 drops of3-isopropenyl-α,α′-dimethylbenzylisocyanate, 10 mL of toluene and 3drops of dibutyltin dilaurate were added. The reaction mixture wasstirred at 90-95° C. for an additional 4 h. The reaction mixture wasallowed to about 40° C. and added slowly to a moderately stirred beakercontaining 125 mL of heptane to precipitate the product. The lightyellow solid was collected by suction filtration, washed with heptaneand allowed to dry on the filter overnight to give 5.49 g of product.The identity of the product was determined to be the target compound byHPLC-MS and the purity was estimated to be about 73%. The compoundexhibited a wavelength of maximum absorption (λ_(max)) at 372.72 nm anda molar absorptivity (c) of 23,900 as determined by Ultraviolet-Visiblelight spectroscopy (UV-Vis) in DMF solvent.

Example 127

To a clean, dry 100 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 40 mL of methanol, 5.88 g ofproduct from Example 117 (30.0 mmols), 2.0 g of malononitrile (30.0mmols) and 5 drops of piperidine. The reaction mixture was heated toreflux with stirring for 1.5 h. Solid product began to form by the timethe reaction had reached reflux. Upon reaction completion, the reactionsolution was allowed to cool to room temperature at which time theproduct began to precipitate. The precipitate was collected by suctionfiltration. The cake was washed with a small amount of chilled methanoland allowed to dry on the filter overnight to give 6.25 g of a freeflowing yellow powder. The compound exhibited a wavelength of maximumabsorption (λ_(max)) at 375.5 nm and a molar absorptivity (c) of 22,300as determined by Ultraviolet-Visible light spectroscopy (UV-Vis) in DMFsolvent.

Example 128

To a clean, dry 100 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 40 mL of acetone, 2.93 g ofproduct from Example 128 (12.0 mmols), 2.5 mL of methacrylic anhydride(16.8 mmols), 2.0 mL of triethylamine (14.4 mmols), 0.07 g of4-dimethylaminopyridine (DMAP, 0.6 mmol) and 40 mg of hydroquinone. Thereaction mixture was heated to 50° C. with stirring for about 30 min atwhich time TLC analysis revealed that all of the starting material(Example 127) had been consumed (TLC; 1:1 tetrahydrofuran/cyclohexane).The reaction mixture was allowed to cool to room temperature thentransferred to a 300 mL flask equipped with a mechanical stirrer. A 3:1(by volume) solution of methanol and water (90 mL), respectively, wasadded with stirring at a dropwise rate followed by the dropwise additionof 60 mL of ice cold water. The product precipitated to give a sticky,but filterable, material. The precipitate was collected by suctionfiltration and washed with a small amount of cold methanol. The cake wasallowed to dry on the filter overnight to give 2.56 g of a yellow solid.The compound exhibited a wavelength of maximum absorption (λ_(max)) at372.7 nm and a molar absorptivity (c) of 14,400 as determined byUltraviolet-Visible light spectroscopy (UV-Vis) in DMF solvent.

Example 129

To a clean, dry 2 L flask equipped with a mechanical stirrer were added100 g of aniline (1.07 mols), 248 mL of benzylchloride (2.16 mols),176.2 g of sodium acetate and 1.0 g of pulverized potassium iodide. Thereaction mixture was heated on a steam bath with stirring overnight. Thereaction mixture was allowed to cool to room temperature then pouredinto a 4 L beaker containing 1 L of ice water and 200 mL of concentratedammonium hydroxide. An oily product came out of solution that solidifiedupon sitting. The solid was collected by suction filtration and washedwith water. The solid was crushed and slurried in methanol. A smallamount of ammonium hydroxide was added then filtered. The resulting cakewas washed with methanol, water and again with methanol. The cake wasallowed to dry on the filter overnight to give 266.3 g of Example 129.The product was recrystallized from 800 mL of isopropyl alcohol to give243.8 g of Example 129 as an off white solid. Field desorption massspectrometry was used to confirm the identity of the product.

Example 130

To a clean, dry 500 mL flask equipped with a heating mantle and additionfunnel were added 150 mL of DMF and 41.0 g of the product from Example129 (0.15 mol). The reaction vessel was purged with nitrogen and 15.4 mLof phosphorus oxychloride (0.15 mol) were added at such a rate to keepthe temperature from exceeding 35° C. The reaction vessel was heated to80-90° C. and stirring for about 2.5 h. The reaction mixture was allowedto cool to room temperature and poured into a mechanically stirred 4 Lbeaker containing ice water mixture (1.2 L) containing 75 mL ofconcentrated ammonium hydroxide. A light tan precipitate formed that wascollected by suction filtration and washed with water. The cake wasallowed to dry on the filter overnight to give 44.8 g of product.

Example 131

To a clean, dry 500 mL round bottomed flask equipped with a magneticstirrer and reflux condenser were added 85 mL of methanol, 4.26 g ofproduct from Example 104 (30.0 mmols), 7.53 g of the product fromExample 130 (25.0 mmols) and a few crystals of piperidine acetate. Thereaction mixture was heated to reflux for 3 h and allowed to cool toroom temperature. The product did not precipitate upon cooling. Thereaction solution was transferred to a Coors dish and the solvent wasallowed to evaporate. The remaining residue solidified upon standing togive 10.7 g of Example 131. The identity of the product was determinedto be the target compound by HPLC-MS and the purity was estimated to beabout 91%. The compound exhibited a wavelength of maximum absorption(λ_(max)) at 380.7 nm and a molar absorptivity (c) of 24,600 asdetermined by Ultraviolet-Visible light spectroscopy (UV-Vis) in DMFsolvent.

Example 132

To a 100 mL round bottomed flask equipped with a magnetic stirrer andheating mantle were added 30 mL of toluene, 1.2 g of3-isopropenyl-α,α′-dimethylbenzylisocyanate (6.0 mmols), 2.06 g of theproduct from example 131 (5 mmols) and 3 drops of dibutyltin dilaurate.The reaction mixture was heated to 90-95° C. After about 1 h, TLCanalysis revealed that some of Example 131 remained (1:1THF/Cyclohexane) and some insoluble material remained that was believedto be starting material. Another 10 mL of toluene were added andstirring was continued at 90-95° C. for an additional 1 h. The reactionmixture was allowed to cool to room temperature and added dropwise to a500 mL beaker containing 40 mL of heptane with stirring to precipitatethe product. An oily material separated. The mother liquor was drownedinto a 500 mL beaker containing 100 mL of ice cold heptane. A soft solidprecipitate formed that was added to fresh, ice cold heptane, which ledto the formation of a hard, filterable solid. The light yellow solid wascollected by suction filtration, washed with cold heptane and allowed todry on the filter overnight to give 0.57 g of product. The identity ofthe product was determined to be the target compound by HPLC-MS and thepurity was estimated to be about 87%. The compound exhibited awavelength of maximum absorption (λ_(max)) at 382.07 nm and a molarabsorptivity (c) of 29,300 as determined by Ultraviolet-Visible lightspectroscopy (UV-Vis) in DMF solvent.

Preparation of Lens Material Example 133 Preparation of Stock MonomerMixture

A stock mixture (50 g) of monomers suitable for preparing intraocularlens material was prepared by thoroughly mixing 2-phenylethyl acrylate(66 weight percent, PEA, CAS#3530-36-7), 2-phenylethyl methacrylate(30.5 weight percent, PEMA, CAS#3683-12-3) and 1,4-butanediol diacrylate(3.5 weight percent, BDDA, CAS#1070-70-8).

Example 134 Control

To a 20 mL vial were added 10 g of the stock mixture and2,2′-azobisisobutyronitrile (52.3 mg, CAS#78-67-1, thermal initiator)then mixed until a solution was obtained. About 2 g of the resultingsolution were added to an 18 mm×150 mm test tube using a syringe.Polymerization was initiated by heating the test tube to 65° C. in avacuum oven under nitrogen for 17 h then heating to 100° C. for anadditional 3 h. The tubes were removed from the oven and allowed to coolto room temperature. The resulting polymer was removed using a spatula.The polymer was placed in a vial containing about 25 mL of acetone andcrushed into small pieces using a spatula. The polymer pieces wereplaced into a Soxhlet extractor and extracted with refluxing acetone for4 to 5 h. The polymer was removed, allowed to dry on a watch glassovernight then dried at 50° C. in a vacuum over at a pressure of about15 mm of Hg for 1 h.

Example 135

To a 20 mL vial were added 10.7 mg of the yellow polymerizable productof Example 107 and 10 g of the stock mixture to give a finalconcentration of about 0.1 weight percent. The mixture was stirred withgentle heating (about 50° C.) until a solution was obtain and allowed tocool to room temperature. A thermal polymerization initiator,2,2′-azobisisobutyronitrile (52.3 mg, CAS#78-67-1), was added and mixeduntil a solution was obtained. About 2 g of the resulting solution wasadded to an 18 mm×150 mm test tube using a syringe. Polymerization wasinitiated by heating the test tube to 65° C. in a vacuum oven undernitrogen for 17 h then heating to 100° C. for an additional 3 h. Thetubes were removed from the oven and allowed to cool to roomtemperature. The resulting polymer was removed using a spatula. Thepolymer was placed in a vial containing about 25 mL of acetone andcrushed into small pieces using a spatula. The polymer pieces wereplaced into a Soxhlet extractor and extracted with refluxing acetone for4 to 5 h. No color was observed in the Soxhlet vessel indicating thatthe yellow compound had polymerized with the monomers duringpolymerization. The polymer was removed, allowed to dry on a watch glassovernight then dried at 50° C. in a vacuum over at a pressure of about15 mm of Hg for 1 h.

Example 136

To a 20 mL vial were added 10.7 mg of the UV light absorbingpolymerizable product of Example 120 and 10 g of the stock mixture togive a final concentration of about 0.1 weight percent. The mixture wasstirred with gentle heating (about 50° C.) until a solution was obtainand allowed to cool to room temperature. A thermal polymerizationinitiator, 2,2′-azobisisobutyronitrile (53.1 mg, CAS#78-67-1), was addedand mixed until a solution was obtained. About 2 g of the resultingsolution were added to an 18 mm×150 mm test tube using a syringe.Polymerization was initiated by heating the test tube to 65° C. in avacuum oven under nitrogen for 17 h then heating to 100° C. for anadditional 3 h. The tubes were removed from the oven and allowed to coolto room temperature. The resulting polymer was removed using a spatula.The polymer was placed in a vial containing about 25 mL of acetone andcrushed into small pieces using a spatula. The polymer pieces wereplaced into a Soxhlet extractor and extracted with refluxing acetone for4 to 5 h. No color was observed in the Soxhlet vessel, indicating thatthe compound had polymerized with the monomers during polymerization.The polymer was removed, allowed to dry on a watch glass overnight thendried at 50° C. in a vacuum over at a pressure of about 15 mm of Hg for1 h.

All patents, publications and abstracts cited above are incorporatedherein by reference in their entirety provided that to the extent anydefinitions in such patents, publications, and abstracts conflict withthose in the present application, the definitions herein shall controlwith respect to the text herein and each conflicting definition in apatent, publication, or abstract shall control with respect to thecontent of the document containing such conflicting definitions. Itshould be understood that the foregoing relates only to preferredembodiments of the present invention and that numerous modifications oralterations can be made therein without departing from the spirit andthe scope of the present invention as defined in the following claims.

1. An intraocular lens comprising a polymer, wherein the polymercomprises at least one residue of a molecule comprising a molecularstructure depicted by Formula 1c:

wherein: X is one or two groups selected from hydrogen, C₁-C₆ alkyl,C₁-C₆ alkoxy and halogen; the molecule has attached thereto at least oneethylenically unsaturated polymerizable group that is not shown byFormula 1c; the residue comprises a reaction product of theethylenically unsaturated polymerizable group; and the moleculeoptionally comprises one or more additional atoms or moieties not shownby Formula 1c.
 2. A compound having the molecular structure of FormulaII:

wherein: R and R₁ are independently selected from C₁-C₁₂-alkyl,substituted C₁-C₁₂-alkyl, aryl, heteroaryl, C₃-C₈-cycloalkyl,C₃-C₈-alkenyl, —(CHR′CHR″O—)_(n)—R₄, C₁-C₆-alkylsulfonyl, arylsulfonyl,C₁-C₁₂-acyl, substituted-C₁-C₁₂-acyl, -L-Q and -Q; or R and R₁ arecombined to make phthalimido, succinimido, morpholino, thiomorpholino,pyrrolidino, piperidino, piperazino, or thiomorpholino-S,S-dioxide; R₂is selected from hydrogen or one or two groups selected from hydroxy,C₁-C₆ alkyl, C₁-C₆ alkoxy and halogen; X₁ is selected from cyano,—CO₂—C₁-C₆-alkyl, C₁-C₆-alkylsulfonyl, arylsulfonyl, carbamoyl,C₁-C₆-alkanoyl, aroyl, aryl, heteroaryl and —COY; X₂ is —COY orcarbamoyl; R′ and R″ are independently selected from hydrogen andC₁-C₁₂-alkyl; Y is selected from —NR′-L-Q, and —N-(L-Q)₂; L is adivalent organic radical selected from C₁-C₆-alkylene-O—,C₁-C₆-alkylene-NR′—; arylene-C₁-C₆-alkylene-O—,arylene-C₁-C₆-alkylene-NR′—, arylene-O(CHR′CHR″O)_(n)—,C₁-C₆-alkylene-Y₁—(CHR′CHR″O—)_(n)—, and —(CHR′CHR″O—)_(n)—; Y₁ isselected from —O—, —S—, —SO₂—, —N(SO₂R₅)—, and —N(COR₅)—; R₄ is selectedfrom hydrogen, C₁-C₁₂-alkyl, C₁-C₆-alkanoyl and aryl; R₅ isC₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl, C₃-C₈-cycloalkyl or aryl; n isan integer from 1 to 100; Q is:

wherein: R₆ is hydrogen or C₁-C₆-alkyl; R₇ is: hydrogen; C₁-C₆ alkyl;phenyl; phenyl substituted with one or more groups selected fromC₁-C₆-alkyl, C₁-C₆-alkoxy, —N(C₁-C₆-alkyl)₂, nitro, cyano,C₁-C₆-alkoxycarbonyl, C₁-C₆-alkanoyloxy and halogen; 1- or 2-naphthyl;1- or 2-naphthyl substituted with C₁-C₆-alkyl or C₁-C₆-alkoxy; 2- or3-thienyl; 2- or 3-thienyl substituted with C₁-C₆-alkyl or halogen; 2-or 3-furyl; or 2- or 3-furyl substituted with C₁-C₆-alkyl; R₈ and R₉are, independently, hydrogen, C₁-C₆-alkyl, or aryl; or R₈ and R₉ arecombined to represent a CH₂₃₋₅ radical; R₁₀ is hydrogen, C₁-C₆-alkyl,C₁-C₈-alkenyl, C₃-C₈-cycloalkyl or aryl; and R₁₁ is hydrogen,C₁-C₆-alkyl or aryl; and the compound comprises at least one Q group. 3.The compound of claim 2, wherein: R and R₁ are independently selectedfrom C₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl, and aryl; or R and R₁ arecombined to make cyclic structures such as phthalimido, succinimido,morpholino, thiomorpholino, pyrrolidino, piperidino, piperazino, orthiomorpholino-S,S-dioxide; R₂ is selected from hydrogen, C₁-C₆ alkyland halogen; X₁ is cyano; X₂ is —COY; Y is selected from —NR′-L-Q, and—N-(L-Q)₂; R′ is selected from hydrogen and C₁-C₁₂-alkyl; L isC₁-C₆-alkylene-O; and Q is:

or —C(O)C(R₆)═CHR₇; wherein R₆ is hydrogen or methyl, R₇ is hydrogen andR₈ and R₉ are methyl.
 4. The compound of claim 2, wherein: R and R₁ areindependently selected from C₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl,aryl, heteroaryl, C₃-C₈-cycloalkyl, C₃-C₈-alkenyl, —(CHR′CHR″O—)_(n)—,C₁-C₆-alkylsulfonyl, arylsulfonyl, C₁-C₁₂-acyl, substituted-C₁-C₁₂-acyl,-L-Q and -Q; or R and R₁ are combined to make phthalimido, succinimido,morpholino, thiomorpholino, pyrrolidino, piperidino, piperazino, orthiomorpholino-S,S-dioxide; R₂ is hydrogen; X₁ is cyano; X₂ is —COY; Yis selected from —NR′-L-Q, —N-(L-Q)₂; R′ is hydrogen; L is selected from—CH₂CH₂—O—, —CH₂CH(CH₃)—O—; n is an integer selected from 1 to 3; and Qis —C(O)C(R₆)═CHR₇, wherein R₆ is methyl and R₇ is hydrogen.
 5. Thecompound of claim 2, wherein: R and R₁ are independently selected frommethyl, ethyl, —CH₂CH₂CN, —CH₂CH₂OCOCH₃, —CH₂CH(CH₃)OCOCH₃; or R and R₁are combined to make thiomorpholino-S,S-dioxide; R₂ is hydrogen; X₁ iscyano; X₂ is —COY; Y is selected from —NR′-L-Q, and —N-(L-Q)₂; R′ ishydrogen; L is selected from —CH₂CH₂—O—, and —CH₂CH(CH₃)—O—; and Q is—C(O)C(R₆)═CHR₇, wherein R₆ is methyl and R₇ is hydrogen.
 6. Thecompound of claim 2, wherein: R and R₁ combined to makethiomorpholino-S,S-dioxide; R₂ is hydrogen; X₁ is cyano; X₂ is —COY; Yis —NR′-L-Q; R′ is hydrogen; L is —CH₂CH(CH₃)—O—; and Q is—C(O)C(R₆)═CHR₇, wherein R₆ is methyl and R₇ is hydrogen.
 7. Thecompound of claim 2, wherein: R and R₁ are independently selected from—CH₂CH₂CN, —CH₂CH₂Cl, —CH₂CH₂—OCO—C₁-C₄-alkyl, —CH₂CH₂OCO-aryl,—CH₂CH₂—OC(O)NH-aryl,

—C₁-C₄-alkyl, and —CH₂C₆H₄CO₂—C₁-C₄-alkyl; or R and R₁ are combined tomake the cyclic structure thiomorpholino-S,S-dioxide; Y is —NH-L-Q; L is—CH₂CH₂O—, —CH₂CH(CH₃)O—, —(CH₂)₃O—, —(CH₂)₄O—, —(CH₂)₆O—,—CH₂C(CH₃)₂CH₂O—, —CH₂—C₆H₁₀—CH₂O—, —C₆H₄—CH₂CH₂O—, —C₆H₄—OCH₂CH₂O—, or—CH₂CH₂(OCH₂CH₂)₁₋₃O—, and Q is

wherein R₆ is methyl; R₈ and R₉ are methyl.
 8. The compound of claim 2,wherein: R and R₁ are independently selected from —CH₂CH₂CN, —CH₂CH₂Cl,—CH₂CH₂—OCO—C₁-C₄-alkyl, —CH₂CH₂OCO-aryl, —CH₂CH₂—OC(O)NH-aryl,

—C₁-C₄-alkyl, and —CH₂C₆H₄CO₂—C₁-C₄-alkyl; or R and R₁ are combined tomake the cyclic structure thiomorpholino-S,S-dioxide; Y is —NH-L-Q; L is—CH₂CH₂O—, —CH₂CH(CH₃)O, —(CH₂)₃O—, —(CH₂)₄O—, —(CH₂)₆O—,—CH₂C(CH₃)₂CH₂O—, —CH₂—C₆H₁₀—CH₂O—, —C₆H₄—CH₂CH₂O—, —C₆H₄—OCH₂CH₂O—, or—CH₂CH₂(OCH₂CH₂)₁₋₃O—; and Q is —C(O)C(R₆)═CHR₇ wherein R₆ is methyl;and R₇ is hydrogen.
 9. The compound of claim 2, wherein: R is —CH₂CH₂CN;R₁ is —CH₂CH₂CN, —CH₂CH₂Cl, —CH₂CH₂OCO—C₁-C₄-alkyl,

Y is —NH-L-Q; L is —CH₂CH₂O— or —CH₂CH(CH₃)O—; and Q is

wherein R₆, R₈ and R₉ are methyl.
 10. The compound of claim 2, wherein:R is —CH₂CH₂CN; R₁ is —CH₂CH₂CN, —CH₂CH₂Cl, —CH₂CH₂OCO—C₁-C₄-alkyl,

Y is —NH-L-Q; L is —CH₂CH₂O— or —CH₂CH(CH₃)O—; and Q is —C(O)C(R₆)═CHR₇;R₆ is methyl; and R₇ is hydrogen.
 11. A compound comprising a molecularstructure depicted by Formula VII:


12. A composition comprising the compound of any one of claims 2-11. 13.A polymer comprising at least one residue of a molecule comprising amolecular structure depicted by Formula 1c:

wherein: X is one or two groups selected from hydrogen, C₁-C₆ alkyl,C₁-C₆ alkoxy and halogen; the molecule has attached thereto at least oneethylenically unsaturated polymerizable group that is not shown byFormula 1c; the residue comprises a reaction product of theethylenically unsaturated polymerizable group; and the moleculeoptionally comprises one or more additional atoms or moieties not shownby Formula 1c.
 14. A polymer comprising at least one residue of amolecule comprising a molecular structure depicted by Formula II:

wherein: R and R₁ are independently selected from C₁-C₁₂-alkyl,substituted C₁-C₁₂-alkyl, aryl, heteroaryl, C₃-C₈-cycloalkyl,C₃-C₈-alkenyl, —(CHR′CHR″O—)_(n)—R₄, C₁-C₆-alkylsulfonyl, arylsulfonyl,C₁-C₁₂-acyl, substituted-C₁-C₁₂-acyl, -L-Q and -Q; or R and R₁ arecombined to make phthalimido, succinimido, morpholino, thiomorpholino,pyrrolidino, piperidino, piperazino, or thiomorpholino-S,S-dioxide; R₂is selected from hydrogen or one or two groups selected from C₁-C₆alkyl, C₁-C₆ alkoxy and halogen; X₁ and X₂ are independently selectedfrom cyano, —CO₂C₁-C₆-alkyl, C₁-C₆-alkylsulfonyl, arylsulfonyl,carbamoyl, C₁-C₆-alkanoyl, aroyl, aryl, heteroaryl and —COY; R′ and R″are independently selected from hydrogen and C₁-C₁₂-alkyl; R₄ isselected from hydrogen, C₁-C₁₂-alkyl, C₁-C₆-alkanoyl and aryl; Y isselected from —O-L-Q, —NR′-L-Q, —N-(L-Q)₂, and —R₅; L is a divalentorganic radical selected from C₁-C₆-alkylene-O—, C₁-C₆-alkylene-NR′—;arylene-C₁-C₆-alkylene-O—, arylene-C₁-C₆-alkylene-NR′—,arylene-O(CHR′CHR″O)_(n)—, C₁-C₆-alkylene-Y₁—(CHR′CHR″O—)_(n)—, and—(CHR′CHR″O—)_(n)—; Y₁ is selected from —O—, —S—, —SO₂—, —N(SO₂R₅)—, and—N(COR₅)—; n is an integer between from 1 to about 1000; R₅ isC₁-C₁₂-alkyl, substituted C₁-C₁₂-alkyl, C₃-C₈-cycloalkyl or aryl; Q is agroup that comprises an ethylenically unsaturated polymerizable group;the molecule, before copolymerization, comprises at least one Q group;the residue comprises a reaction product of saturation of the Q group;and the molecule optionally comprises one or more additional atoms ormoieties not shown by Formula II.
 15. A composition comprising thepolymer of claim
 13. 16. A composition comprising the polymer of claim14.
 17. A method of making a polymer, comprising copolymerizing monomerswherein the monomers comprise the compound(s) of any of claims 2-11.